TW200304238A

TW200304238A - Improved polymer buffer layers and their use in light-emitting diodes

Info

Publication number: TW200304238A
Application number: TW092104248A
Authority: TW
Inventors: Che-Hsiung Hsu
Original assignee: Du Pont
Priority date: 2002-02-28
Filing date: 2003-02-27
Publication date: 2003-09-16
Also published as: CA2476752A1; US20030222250A1; US6955773B2; KR20040096552A; US7038375B2; JP2005519440A; CN1630951A; AU2003213279A1; WO2003075370A2; US20050263781A1; WO2003075370A3; EP1479113A2

Abstract

The present invention is directed to improved transparent electrically conductive buffer layers for light-emitting diodes. The use of an aqueous dispersion containing an electrically conducting polymer and a non-ionic surfactant or an ionic fluorosurfactant to form the buffer layer has been shown to provide a buffer layer that results in improved light-emitting diode performance.

Description

200304238 ⑴ 玫、發明說明 (發明說明i敘明:發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明) 技術領域本發明係關於由導電聚合物和界面活性劑組成之透明導電緩衝層以及含此層之發光裝置。 a前技術已發現導電？長合物用於發光的有機電子裝置，如發光二極體（LEDs)。在所有此等裝置中，有機活性發射層夾在充當 1%極和陰極的兩個電極之間。至少一個電極由透光材料組成。在對裝置施加電壓時，活性發射層通過透光電極發光， —般通過氧化錫錮陽極。在無機陽極和發光層之間使用導電聚合物層已為吾等所熟悉，如聚苯胺或聚（二氧噻吩）。導電聚合物層被不同稱為陽極部分、空穴注射層或緩衝層。例如’此等系統已描述於詹奈斯（J〇nas)等人的美國專利第 5,766,5 15號、揚（Yang)的美國專利第5,723,783號及章（zhang) 等人的美國專利第5,798，170號。用於製備聚苯胺（PAni)或聚（二氧噻吩）[如聚（3,4-伸乙基 ~氧嘧吩）（PEDOT)]之合成步騾係為已知，且此等材料易於購得。慶林（Kinlen)等人的美國專利第5,84〇,214號揭示一種增加氷苯胺導電性之方法，其包括使聚苯胺與一種離子性界面活&彳華觸。慶林等人說明一種形成聚苯胺薄膜及隨後使-p二永苯胺薄膜與一種離子性界面活性劑接觸之方法。他們亦揭示，在聚苯胺鹽與陰離子性界面活性劑二者以至少約i 重量％之I對各聚苯胺鹽和離子性界面活性劑可溶時，可 200304238 (2) 發明說明續筲在加工成最終形態之前在二甲苯中處理聚苯胺鹽。所以，理想發現一種提供較佳性能的具有電特性之聚合物，該聚合物在發光裝置中作為缓衝層。發明内容本發明在基材上提供一種發光裝置。該發光裝置包括一陽極、一陰極、一位於該陽極及陰極間之活性發射層以及一位於該陽極和活性發射層間之缓衝層。其中該缓衝層由導電聚合物及界面活性劑組成。以該界面活性劑和導電聚合物之總重量計，該界面活性劑之量係自約0.5重量％至約· 15重量％，且該界面活性劑係選自含氟界面活性劑、聚氧伸乙基烷基酚醚或其混合物。本發明亦在基材上提供一種發光裝置，該發光裝置包括一陽極、一陰極、一位於該陽極及陰極間之活性發射層以及一位於_該陽極和活性發射層間之缓衝層。其中該緩衝層用已加入一種界面活性劑之導電聚合物之水性分散液形成。該分散液特徵為介於2 5和3 5毫牛頓/米之表面張力。以全部分散液計，該導電聚合物之濃度係自〇.1重量％至5.0重量。/。。以全部分散液計，該界面活性劑之濃度小於約0.4重量％，且界面活性劑係選自含氟界面活性劑、聚氧伸乙基燒基驗酸或其混合物。使用本發明之緩衝層亦使利用由金屬層和薄無機介電層-組成的光傳輸雙層陽極且介電層與緩衝層相鄰成為可能。本發明亦提供用於形成位於發光裝置之陽極和陰極間之緩衝層之組合物’該組合物包括已加入一種界面活性劑之 200304238 (3) 發明就胡續筲導電聚合物之水性分散液。該分散液特徵為介於25和35毫牛頓/米之表面張力。以全部分散液計，該導電聚合物之濃度係自〇· 1重量％至5.0重量％。以全部分散液計，該界面活性劑之濃度小於約0.4重量％，且界面活性劑係選自含氟界面活性劑、聚氧伸乙基燒基S分醚或其混合物。在本文中，’’全部分散液”表示分散液之全部固體和液態載劑。此外，遍及本文使用IUPAC編號系統，自周期表的各族自左至右編為1至18族[CRC物理化學手冊（CRC Handbook of Chemistry and Physics)，81以版，2000]。短語”相鄰”不一定· 指一層直接與另一層相鄰。可在被稱為相互相鄰的層間提供中間層。實施方式本發明係關於在發光裝置中形成提供較佳性能之導電聚合物層作—為缓衝層。已發現，用由導電聚合物和特定界面活性劑組成的組合物及因此由此等相同組分組成的組合物形成之緩衝層提供具有所需改良性能之緩衝層。可將界面活性劑認作為不利影響裝置性能之雜質。令人驚詩的是，此等特定界面活性劑（即，含氟界面活性劑或聚氧伸乙基燒基酚醚）不僅促進塗覆水性分散液以形成緩衝層，而且改良裝置性能並有利於使用柔韌性基材。為顯示改良的性能，作為發光裝置部分評估缓衝層很關鍵。本發明亦關於一種發光裝置，其包括夾在兩個電接觸層間之有機活性發射層，其中一包含導電聚合物和界面活性劑之緩衝層位於發光層和作為陽極的電接觸層之間。該裝 200304238 發明餽明續賓· (4) 置具有無機陽極層和陰極層。與陽極層相鄰的為緩衝層。與陰極相鄰的為包含電子傳輸物質之選擇性層。介於該緩衝層和陰極（或選擇性電子傳輸層）間的為活性發射層。該裝置一般亦包括可與該陽極或陰極相鄰之載體。載體最通常與陽極相鄰。載體可為柔韌性或剛性、有機或無機材料。一般用玻璃或柔韌性有機薄膜作為載體，如聚（對酞酸乙二醇酯）。陽極為對注射或收集正電荷載體特別有效的電極。陽極可為金屬、混合金屬、合金、金屬氧化物或混合金屬氧化物。適合金屬包括第11族金屬、第4、5和6族金屬以及第8-10 族過渡金屬。如果欲使陽極透光，一般使用第12、13和14 族金屬之混合金屬氧化物，如氧化錫銦。使用本發明之缓衝層亦使利用由金屬層和薄無機介電層組成的光傳輸雙層陽極且介電層與緩衝層相鄰成為可能。可在沈積金屬層之前使額外薄介電層沈積於基材上。亦可使用由二或更多金屬和電介質之雙層組成的多層陽極，即，金屬-電介質-金屬-電介質等。雙層中的金屬由銀、金、鎳、絡、姑、其合金及此等金屬與鐵之合金組成。雙層中的電介質由第13或14族元素（如，石夕、銦、鈥、錫、鍺和鋁）之氧化物或氟化物（如氟化鎂）組成。在一較佳具體實施例中，緩衝層直接提供於含至少一個雙層之多層陽極之介電— 層上。陽極通常由物理蒸氣沈積方法施加。π物理蒸氣沈積"指在真空中實施的各種沈積方法。因此，例如，物理蒸氣沈 200304238200304238 ⑴ Rose, description of the invention (Invention description i: the technical field to which the invention belongs, the prior art, content, embodiments, and a brief description of the drawings) TECHNICAL FIELD The present invention relates to a transparent conductive composition composed of a conductive polymer and a surfactant. Buffer layer and light emitting device containing the same. aPrevious technology Has been found conductive? Long compounds are used in light-emitting organic electronic devices, such as light-emitting diodes (LEDs). In all of these devices, the organic active emission layer is sandwiched between two electrodes acting as a 1% pole and a cathode. At least one electrode is composed of a light-transmitting material. When a voltage is applied to the device, the active emission layer emits light through the light-transmitting electrode, typically through a tin oxide / anode. The use of conductive polymer layers between inorganic anodes and luminescent layers is familiar to us, such as polyaniline or poly (dioxythiophene). The conductive polymer layer is referred to differently as the anode portion, the hole injection layer, or the buffer layer. For example, 'these systems have been described in US Pat. No. 5,766,515 of Jonas et al., US Pat. No. 5,723,783 of Yang and US Pat. No. 5,798 of Zhang et al. No. 170. Synthetic steps for preparing polyaniline (PAni) or poly (dioxythiophene) [such as poly (3,4-ethylidene ~ oxopyrimidine) (PEDOT)] are known, and these materials are easy to purchase Got. Kinlen et al., U.S. Patent No. 5,84,0,214, discloses a method for increasing the conductivity of ceanilide, which comprises activating & catalyzing polyaniline with an ionic interface. Qinglin et al. Described a method for forming a polyaniline film and subsequently contacting a -p di-n-aniline film with an ionic surfactant. They also revealed that when both the polyaniline salt and the anionic surfactant are soluble in each of the polyaniline salt and the ionic surfactant with at least about i wt% of I, 200304238 (2) Description of the invention continued. The polyaniline salt was treated in xylene before reaching the final form. Therefore, it is desirable to find a polymer having electric characteristics which provides better performance, and the polymer serves as a buffer layer in a light emitting device. SUMMARY OF THE INVENTION The present invention provides a light emitting device on a substrate. The light emitting device includes an anode, a cathode, an active emission layer between the anode and the cathode, and a buffer layer between the anode and the active emission layer. The buffer layer is composed of a conductive polymer and a surfactant. Based on the total weight of the surfactant and the conductive polymer, the amount of the surfactant is from about 0.5% to about 15% by weight, and the surfactant is selected from the group consisting of a fluorinated surfactant and a polyoxyethylene Ethyl alkyl phenol ether or mixtures thereof. The present invention also provides a light emitting device on a substrate. The light emitting device includes an anode, a cathode, an active emission layer located between the anode and the cathode, and a buffer layer located between the anode and the active emission layer. The buffer layer is formed using an aqueous dispersion of a conductive polymer to which a surfactant has been added. The dispersion is characterized by a surface tension between 25 and 35 millinewtons / meter. The concentration of the conductive polymer is from 0.1% by weight to 5.0% by weight based on the entire dispersion. /. . The concentration of the surfactant is less than about 0.4% by weight based on the entire dispersion, and the surfactant is selected from the group consisting of a fluorinated surfactant, a polyoxyethylene acid test, or a mixture thereof. Using the buffer layer of the present invention also makes it possible to use a light-transmitting double-layer anode consisting of a metal layer and a thin inorganic dielectric layer, with the dielectric layer adjacent to the buffer layer. The present invention also provides a composition for forming a buffer layer between an anode and a cathode of a light-emitting device. The composition includes 200304238 to which a surfactant has been added. (3) The invention discloses an aqueous dispersion of a conductive polymer. The dispersion is characterized by a surface tension between 25 and 35 millinewtons / meter. The concentration of the conductive polymer is from 0.1% to 5.0% by weight based on the entire dispersion. The concentration of the surfactant is less than about 0.4% by weight based on the entire dispersion, and the surfactant is selected from the group consisting of a fluorine-containing surfactant, a polyoxyethylene sulfenyl ether, or a mixture thereof. In this text, "total dispersion" means all solid and liquid carriers of the dispersion. In addition, throughout the text, the IUPAC numbering system is used, and each group of the periodic table is grouped from left to right into groups 1 to 18 [CRC Handbook of CRC (Handbook of Chemistry and Physics), Issue 81, 2000]. The phrase "adjacent" does not necessarily mean that one layer is directly adjacent to another. Intermediate layers can be provided between layers called adjacent ones. Implementation The present invention relates to the formation of a conductive polymer layer in a light-emitting device that provides better performance as a buffer layer. It has been found that a composition consisting of a conductive polymer and a specific surfactant is used and therefore the same group The buffer layer formed by the component composition provides a buffer layer with desired improved properties. Surfactants can be considered as impurities that adversely affect device performance. Surprisingly, these specific surfactants (i.e., containing Fluorosurfactant or polyoxyethylene ethyl phenol ether) not only facilitates the coating of aqueous dispersions to form a buffer layer, but also improves device performance and facilitates the use of flexible substrates. As a part of the light-emitting device, it is critical to evaluate the buffer layer. The present invention also relates to a light-emitting device that includes an organic active emitting layer sandwiched between two electrical contact layers, one of which contains a conductive polymer and a surfactant buffer. The layer is located between the light-emitting layer and the electrical contact layer serving as the anode. The device 200304238 invention Mingming continued · (4) The device has an inorganic anode layer and a cathode layer. The buffer layer adjacent to the anode layer is adjacent to the cathode. A selective layer containing an electron-transporting substance. An active emission layer is interposed between the buffer layer and the cathode (or selective electron-transporting layer). The device also generally includes a carrier that can be adjacent to the anode or cathode. The carrier is most It is usually adjacent to the anode. The carrier can be flexible or rigid, organic or inorganic materials. Generally, glass or flexible organic film is used as the carrier, such as poly (ethylene terephthalate). The anode is a positive charge for injection or collection. Carrier particularly effective electrode. The anode can be metal, mixed metal, alloy, metal oxide or mixed metal oxide. Suitable metals include Group 11 metals, Groups 4, 5 and 6 metals and Groups 8-10 transition metals. If the anode is to be transparent, mixed metal oxides of Groups 12, 13 and 14 metals, such as indium tin oxide, are generally used. Use the buffer of the present invention The layer also makes it possible to use a light-transmitting double-layer anode consisting of a metal layer and a thin inorganic dielectric layer with the dielectric layer adjacent to the buffer layer. An additional thin dielectric layer can be deposited on the substrate before the metal layer is deposited. It is also possible to use a multilayer anode consisting of two or more layers of two layers of metal and dielectric, i.e. metal-dielectric-metal-dielectric, etc. The metal in the double layer is composed of silver, gold, nickel, complex, alloy, and alloy It is composed of an alloy of metals and iron. The dielectric in the double layer is composed of oxides or fluorides (such as magnesium fluoride) of Group 13 or 14 elements (such as Shixi, Indium, ', tin, germanium, and aluminum). In a preferred embodiment, the buffer layer is provided directly on the dielectric-layer of the multilayer anode including at least one double layer. The anode is usually applied by a physical vapor deposition method. π physical vapor deposition " refers to various deposition methods performed in a vacuum. So, for example, physical vapor sink 200304238

積包括所有形式的丨賤鍍（包括離子束錢鍵）及所有形式的1 氣沈積（如電子束蒸發）。所用物理蒸氣沈積的具體形式為射頻磁控管濺鐘。該緩衝層可用任何習知方法施加，包括旋塗、澆轉和印刷（如，凹版印刷）。緩衝層亦可由噴墨印刷或熱圖案化施加。用形成位於發光裝置陽極和活性發射層間之緩衝I< 本發明組合物包括已加入界面活性劑之導電聚合物之水性分散液。導電聚合物較佳為聚苯胺（PAni)或聚（二氧魂吩）。較佳聚（二氣ρ塞吩）為聚（3,4-伸乙基二氧p塞吩）（PED〇T)。用於_ 製造聚苯胺或聚（二氧嘍吩）之氧化聚合方法在聚（丙缔醯胺基烷基磺酸）(PAAMPSA)或聚（笨乙烯磺酸）（PSSA)存在下進行，並產生多種錯合物，如PEDOT/PAAMPSA、PEDOT/PSSA、 Pani/PAAMPS A 及 PAni/PS S A。在本文中，聚苯胺（PAni)、聚（二氧魂吩）和聚（3,4-伸乙基二氧嘍吩）分別指聚合物自身及由該聚合物組成之錯合物。界面活性劑為含默界面活性劑或聚氧伸乙基烷基酚醚。界面活性劑可為非離子性界面活性劑（即，非離子性含氟界面活性劑或聚聚氧伸乙基烷基酚醚）或離子性含氟界面活性劑。較佳使用非離子性界面活性劑。較佳聚氧伸乙基烷基酝醚為桌氧伸乙基（10)異辛基苯基醚。非離子性含氟界面活性劑較佳為氟脂，系聚合自旨或含具式F(CF2CF2)3 8之全氟燒_ 基之含氟界面活性密丨|。λ ^ "，J 尤佳為全氟烷基聚氧伸乙基。離子性含氟界面活性劑較佳包含具有式F(cF2CF2)3 k全敗院基尤佳為王氟认基伸乙基硫伸乙基陰離子界面活性劑之 200304238 (6) I發明說钥續霣碳酸鋰鹽。亦可使用兩性界面活性劑（如全氟烷基N-類型甜菜鹼）及陽離子性界面活性劑（如，全氟烷基i化銨）。The product includes all forms of base plating (including ion beam money bonds) and all forms of gas deposition (such as electron beam evaporation). The specific form of physical vapor deposition used is a radio frequency magnetron splash clock. The buffer layer can be applied by any conventional method, including spin coating, casting, and printing (e.g., gravure printing). The buffer layer may also be applied by inkjet printing or thermal patterning. A buffer I formed between the anode of the light emitting device and the active emission layer is used to form an aqueous dispersion of a conductive polymer to which a surfactant has been added. The conductive polymer is preferably polyaniline (PAni) or poly (dioxin). A preferred poly (digas p-phene) is poly (3,4-ethylenedioxy p-phene) (PEDOT). The oxidative polymerization method used for the manufacture of polyaniline or poly (dioxophene) is carried out in the presence of poly (propyleneiminoaminosulfonic acid) (PAAMPSA) or poly (benzyl ethylenesulfonic acid) (PSSA), and A variety of complexes are produced, such as PEDOT / PAAMPSA, PEDOT / PSSA, Pani / PAAMPS A, and PAni / PS SA. In this paper, polyaniline (PAni), poly (dioxophene), and poly (3,4-ethylenedioxophene) refer to the polymer itself and the complex consisting of the polymer, respectively. The surfactant is a melamine-containing surfactant or a polyoxyethylene alkyl phenol ether. The surfactant may be a non-ionic surfactant (i.e., a non-ionic fluorine-containing surfactant or a polyoxyethylene ethyl phenol ether) or an ionic fluorine-containing surfactant. Preferably, a non-ionic surfactant is used. A preferred polyoxyethylene alkyl ether is oxyethyl (10) isooctylphenyl ether. The nonionic fluorine-containing interfacial active agent is preferably a fluorolipid, which is a polymerization purpose or a fluorine-containing interfacial active density containing a perfluorocarbon group of formula F (CF2CF2) 38. λ ^ ", J is particularly preferably a perfluoroalkyl polyoxyethylene. The ionic fluorine-containing surfactant preferably contains a formula of F (cF2CF2) 3 k. It is particularly preferred to be a fluorocarbon-based ethyl sulfide ethyl anionic surfactant. 200304238 (6) I Invention Key Continued Carbonic Acid Lithium salt. Amphoteric surfactants (such as perfluoroalkyl N-type betaine) and cationic surfactants (such as perfluoroalkylammonium iodide) can also be used.

以全部分散液計，該導電聚合物之濃度係自〇. 1重量％至 5.0重量％。以全部分散液計，該界面活性劑之濃度小於約 0.4重量％。以全部分散液計，該導電聚合物之濃度較佳自 0.5重量％至3.0重量％，而該界面活性劑之濃度以全部分散液計小於約0.3重量％。所用特定界面活性劑之量依賴所用特定導電聚合物及該導電聚合物在分散液中的濃度。應選擇界面活性劑之量，以提供於25和35毫牛頓/米間之分散液表面張力。本發明提供一種發光裝置，其中該緩衝層用包含導電聚合物之水性分散液之組合物製造，且該導電聚合物之水性分散液已如先前段落所述加入一種界面活性劑。The concentration of the conductive polymer is from 0.1% to 5.0% by weight based on the entire dispersion. The concentration of the surfactant is less than about 0.4% by weight based on the entire dispersion. The concentration of the conductive polymer is preferably from 0.5% to 3.0% by weight based on the total dispersion, and the concentration of the surfactant is less than about 0.3% by weight based on the total dispersion. The amount of the specific surfactant used depends on the specific conductive polymer used and the concentration of the conductive polymer in the dispersion. The amount of surfactant should be selected to provide a dispersion surface tension between 25 and 35 mN / m. The present invention provides a light emitting device, wherein the buffer layer is made of a composition containing an aqueous dispersion of a conductive polymer, and a surfactant is added to the aqueous dispersion of the conductive polymer as described in the previous paragraph.

本發叽之發光裝置之緩衝層由導電聚合物及界面活性劑組成，其中以該界面活性劑和導電聚合物之總重量計，該界面活性劑之量係自約0.5重量％至約15重量％。界面活性劑為如與本發明組合物有關所述的含氟界面活性劑或聚氧伸乙基燒基驗醚。以該界面活性劑和導電聚合物之總重量計，該界面活性劑之量較佳自約1重量％至約10重量％。陽極和導電聚合物層一般經圖案化。應瞭解，圖案可視需要變化。為以圖案形式施加該層，例如，可在施加第一-電接觸層材料之前將圖案化罩幕或光阻劑佈置於第一柔韌性複合障壁結構上。或者，將該層作為整體層施加，隨後用（例如）光阻劑和濕化學蚀刻圖案化。如上所討論，亦可由 -10 - 200304238The buffer layer of the light emitting device of the present invention is composed of a conductive polymer and a surfactant, wherein the amount of the surfactant is from about 0.5% by weight to about 15% by weight based on the total weight of the surfactant and the conductive polymer. %. The surfactant is a fluorine-containing surfactant or polyoxyethylene ethyl ether as described in connection with the composition of the present invention. The amount of the surfactant is preferably from about 1% by weight to about 10% by weight based on the total weight of the surfactant and the conductive polymer. The anode and conductive polymer layers are generally patterned. It should be understood that the pattern can be changed as needed. To apply the layer in a pattern, for example, a patterned mask or photoresist may be disposed on the first flexible composite barrier structure before the first-electric contact layer material is applied. Alternatively, the layer may be applied as a monolithic layer and subsequently patterned with, for example, a photoresist and wet chemical etching. As discussed above, -10-200304238

加緩衝層。 ⑺ 噴墨印刷、微影或熱轉移圖案化以圖案形式施亦可使用技藝上熟悉的其他用於圖案化之方法。在一發光二極體中，在對電接觸層（即，陽極和陰極）施加足夠偏壓時活性發射層發光。發光活性發射層可包冬有機電冷光或其他有機發光物質。此等物質可為小分子物質，如唐（Tang)美國專利第4,356,429號、萬-斯菜克（Van Slyke)等人美國專利第4,539,507號所述者，其相關部分係以引用之方式併入本文中。具有由小分子（SMO)組成活性發射層之LEDs 一般被稱為SMOLEDs。或者，此等物質可為聚合性物質，-如弗阮德（Friend)等人（美國專利第5,247，19〇號）、赫格（Heeger) 等人（美國專利第5,408,109號）、奈克諾（Nakano)等人（美國專利第5,3 17,169號）所述者，其相關部分係以引用之方式併入本文中。具有由聚合性（P)物質組成活性發射層之LEDs一般被稱為PLEDs。較佳電冷光物質為半導性共軛聚合物。此等聚合物之實例為聚（對伸苯基伸乙烯基），稱為ppv。可在具有和不具有添加劑下使發光物質分散於另一種物質之基質中’但較佳單獨形成層。活性有機層一般具有在50-500奈米範圍 < 厚度。為抑制圖案化陽極的線或像素之間的_話，緩衝層的電導性應盡可能低，且不應危害裝置的發光性月匕已發現，當緩衝層包含導電聚合物和為含氟界面活性「申乙基坑基盼鍵的界面活性劑時，與缓衝層包含- 導電聚合物而I R^ ”、、界面活性劑比較，發光二極體顯示較高發光效率、相當或較低接通電壓及相當或較高亮度。。’舌性有機物質之活性發.射層可由任何習知方法自溶液 200304238 ⑻ _ ^ 11¾¾¾ 施加，包括旋塗、澆鑄和印刷。活性 ^ 性質可直接由蒸氣沈積方法施加1 ’物質依賴該物質驅體，然後轉化成聚合物，—般由加熱她力σ活性聚合物前陰極為對注射或收集電子或符人/、私何載體特極。陰極可為比第一電接觸層（在此情有Α勺私从S 士八iA人您 /下為陽極）具有較低功里4金屬或非金屬。用於第：電物質可選自篇1 族驗金屬（例如，u，Cs)、第2族（驗土、、 )隹屬、第12族金屬、鑭系兀素及婀第元素。可使用如鋁、所絪、鈣、鋇和鎂之物、及其組合。陰極層通常由物理蒸氣沈積方 L万忐她加。一般使陰極層圖术化，如以上關於陽極層和緩衝芦衡層又纣論。可用類似處理技術使陰極層圖案化。陰極和活性發射層間之選擇性芦生層了促進電子傳輸，亦可作為限制層防止在層界面反應中丨。該層較佳促進電子流動性，並減少中止反應。用於選擇性層的電子傳輸物質之實例包括’金屬螯合經,套類化合物，如畚(8_羥基峻琳根) 合鋁（Alq3);以菲咯啉為基礎的化合物，如2,9•二甲基_4,7-二苯基-ι，ιο-菲咯啉（DDPA)或4,7二苯基'1〇_菲咯啉（DpA); 及唑類化合物，如2_(4-聯苯基）_5_(4·第三丁基苯基^义心噁一唑（PBD)及3-(4-聯苯基）-4-苯基-5-(4-第三丁基苯基卜丨，2,4· ***（ΤΑΖ)。已决在有機電子裝置中有其他層。例如，可在緩衝層和活性發射層 < 間有一層促進層的正電荷傳輸和/或帶隙匹配或作為保護層。類似可在活性發射層和陰極層之間有一 -12- (9)200304238Add a buffer layer. ⑺ Ink-jet printing, lithography, or thermal transfer patterning is applied as a pattern. Other methods for patterning that are familiar in the art can also be used. In a light emitting diode, the active emission layer emits light when a sufficient bias is applied to the electrical contact layers (i.e., the anode and the cathode). The luminescent active emission layer can include winter organic electroluminescent or other organic light-emitting substances. These substances may be small molecule substances, such as those described in Tang US Patent No. 4,356,429, Van Slyke, et al. US Patent No. 4,539,507, the relevant portions of which are incorporated by reference In this article. LEDs with active emitting layers composed of small molecules (SMO) are commonly referred to as SMOLEDs. Alternatively, such substances may be polymerizable substances, such as Friend et al. (US Patent No. 5,247,190), Heeger et al. (US Patent No. 5,408,109), Nekerno (Nakano) et al. (US Patent No. 5,3 17,169), the relevant parts of which are incorporated herein by reference. LEDs with active emitting layers composed of polymerizable (P) substances are generally referred to as PLEDs. A preferred electroluminescent material is a semiconductive conjugated polymer. An example of such a polymer is poly (p-phenylene vinylene), called pPV. The luminescent substance can be dispersed in a matrix of another substance with and without additives', but it is preferred to form the layer separately. The active organic layer generally has a thickness in the range of 50-500 nm. In order to suppress the pattern between the lines or pixels of the patterned anode, the conductivity of the buffer layer should be as low as possible and should not endanger the luminescence of the device. It has been found that when the buffer layer contains a conductive polymer and is a fluorine-containing interface When activating the "surfactant for ethyl pentyl bond", compared with the buffer layer containing-conductive polymer and IR ^ ", the surfactant shows that the light-emitting diode shows higher luminous efficiency, equivalent or lower on-voltage And comparable or higher brightness. . The active hair of lingual organic materials. The spray layer can be applied from solution 200304238 by any conventional method. ^ ^ 11 ¾ ¾ ¾, including spin coating, casting and printing. Reactive properties can be directly applied by the vapor deposition method. 1 'Substance depends on the substance to drive the body, and then converted into polymers, generally by heating the force σ active polymer front cathode for injection or collection of electrons or fu / human Carrier Extreme. The cathode may be lower than the first electrical contact layer (in this case, AA, S / A, i / A, A / A, A / A) and a metal or nonmetal. Substances used in Group: Electricity may be selected from Group 1 metal test (eg, u, Cs), Group 2 (earth test, 隹) genus, Group 12 metals, lanthanide, and ytterbium. Things such as aluminum, aluminum, calcium, barium, and magnesium, and combinations thereof can be used. The cathode layer is usually deposited by physical vapor deposition. The cathode layer is generally patterned, as discussed above about the anode layer and the buffer layer. The cathode layer can be patterned using similar processing techniques. The selective growth layer between the cathode and the active emission layer promotes electron transport and also acts as a confinement layer to prevent reactions at the layer interface. This layer preferably promotes electron mobility and reduces stop reactions. Examples of the electron-transporting substance for the selective layer include a metal chelation compound, a set of compounds such as europium (8-hydroxyjunline) aluminum (Alq3); a phenanthroline-based compound such as 2, 9 • dimethyl_4,7-diphenyl-ι, ιο-phenanthroline (DDPA) or 4,7 diphenyl'1__phenanthroline (DpA); and azole compounds such as 2_ ( 4-biphenyl) _5_ (4 · Third-butylphenyl ^ sense isoxazole (PBD) and 3- (4-biphenyl) -4-phenyl-5- (4-tert-butyl Phenylbenzene, 2,4 · triazole (TAZ). Other layers have been determined in organic electronic devices. For example, there may be a layer between the buffer layer and the active emission layer < to promote the positive charge transport of the layer and / or Band gap matching or as a protective layer. Similarly, there can be a -12- (9) 200304238 between the active emission layer and the cathode layer

額外層促進層的負電荷保護層。可使用技藝上或更多層組成。或者，傳輸和/或在層間帶隙匹配或作為已知多種層。此外，上述層可由二可表面處理所有或一些陽極層、緩衝層、活性發射層釦^ & 年陰極層，以增加電荷載體傳輸效率。對各組分層的材料姐竹域擇較佳由平衡提供具有高裝置效率之裝置之目標決定。可由在適合基材上順序沈積各單獨層製備該裝置。可使用如玻璃和汆合物薄膜之基材。在大多數情況下，將陽極犯加到基材，並自其建立各層。但可首先將陰極施加到基_ 材並以反向順序施加各層。不同層一般具有以下範圍厚度·陽極，50-500奈米，較佳1〇〇_2〇〇奈米；緩衝層，5_25〇奈米’較佳20-200奈米；發光活性發射層，丨-⑽奈米，較佳 10 80奈米，選擇性電子傳輸層，5_1〇〇奈米，較佳奈米；陰極，20_-1000奈米，較佳3〇-5〇〇奈米。實例以下實例說明本發明的某些特徵及優點。它們為本發明之說明，而非限制。除非另外指明，所有百分比均以重量計。本文報告的所有表面張力測量用數位克魯斯處理張力儀 (Digital Kriiss Process Tensiometer) K12 (Kruss GmbH? Hamburg,The extra layer promotes the negative charge protection layer of the layer. You can use technically or more layers. Alternatively, transmission and / or band gap matching between layers or as multiple layers are known. In addition, the above layers can be surface treated with all or some of the anode layer, buffer layer, and active emission layer and the cathode layer to increase the charge carrier transfer efficiency. The best choice of material for each component layer is determined by the goal of balancing and providing a device with high device efficiency. The device can be prepared by sequentially depositing individual layers on a suitable substrate. Substrates such as glass and admixture films can be used. In most cases, anodes are added to the substrate and layers are built from it. But the cathode can be applied to the substrate first and the layers applied in reverse order. Different layers generally have the following thicknesses: anode, 50-500 nanometers, preferably 100-200 nanometers; buffer layer, 5-25 nanometers, preferably 20-200 nanometers; luminescent active emission layer, 丨-Nanometer, preferably 10 to 80 nanometers, selective electron transport layer, 5 to 100 nanometers, preferably nanometer; cathode, 20 to 1000 nanometers, preferably 30 to 500 nanometers. Examples The following examples illustrate certain features and advantages of the invention. They are illustrative and not restrictive. Unless otherwise indicated, all percentages are by weight. Digital Kriiss Process Tensiometer K12 (Kruss GmbH? Hamburg,

Germany)進行。測量在室溫完成。含欲經測量液體之容器具有6.65爱米直徑和10.0复米高度。測量方法為克魯斯n (P/SFT)，最小標準偏差為0.02毫牛頓/米。本文報告的對柔勃性發光二極體（LEDs)(即，柔勃性基材 13 200304238 (ιο) 1 nwm 上的發光一極體）之發光測量用以下方式進行。用於發光測量之柔勃性LED樣品由柔勃性基材、作為陽極的氧化錫銦層、緩衝層、活性發射物質層及作為陰極的1 〇毫米直徑銘點陣列。將HP 4155A半導體參數分析儀（Hewlett-Packard，Palo Alto，CA)之可程式化電壓源用對電極提供壓力接觸之機械裝置連接到陽極和一鋁點。發光用光電二極體檢測，並由此轉化成記錄發光強度的電流。在對電極施加的電壓自動向上步進時，連續記錄裝置電流及光電二極體電流。本文報告的對剛性發光二極體（LEDs)(即，剛性基材上發-光二極體，例如玻璃基材）之發光測量用以下方式進行。用於發光測量之剛性LED樣品如對柔韌性LEDs所述進行，但基材由剛性（玻璃）基材形成。電流-電壓、發光強度（亮度）_電壓和效率（坎德拉/安培）用凱斯利（Keithley) 236源測量裝置 (俄亥俄州’克利夫蘭’凱斯利儀器公司）（Keithley Instrument Inc.，Cleveland，OH)以及具有經校準矽光電二極體之S37〇視力計（加利福尼亞州，夏松，UDT感測器公司）（UDT Sensor，Inc， Hawthorne, CA)檢測。除非另外指明，所有檢測均於約2〇°c室溫進行。Germany). The measurement was completed at room temperature. The container containing the liquid to be measured has a diameter of 6.65 m and a height of 10.0 m. The measurement method is Cruise N (P / SFT) with a minimum standard deviation of 0.02 millinewtons / meter. The luminescence measurement of flexible light-emitting diodes (LEDs) (ie, light-emitting diodes on flexible substrates 13 200304238 (ιο) 1 nwm) reported in this paper was performed in the following manner. The flexible LED samples used for luminescence measurement consist of a flexible substrate, an indium tin oxide layer as an anode, a buffer layer, an active emitting material layer, and a 10 mm diameter dot array as a cathode. The programmable voltage source of the HP 4155A Semiconductor Parameter Analyzer (Hewlett-Packard, Palo Alto, CA) was connected to the anode and an aluminum point using a mechanism that provided pressure contact to the electrode. Luminescence is detected by a photodiode and is thereby converted into a current that records the intensity of the luminescence. When the voltage applied to the electrode is automatically stepped up, the device current and the photodiode current are continuously recorded. The luminescence measurements on rigid light-emitting diodes (LEDs) (ie, light-emitting diodes on rigid substrates, such as glass substrates) reported herein are performed in the following manner. Rigid LED samples for luminescence measurements were performed as described for flexible LEDs, but the substrate was formed from a rigid (glass) substrate. Current-Voltage, Luminous Intensity (Brightness) _Voltage and Efficiency (Candela / Amp) Keithley 236 Source Measurement Device ('Cleveland, Ohio' Kesley Instrument Company) (Keithley Instrument Inc., Cleveland, OH ) And an S370 ophthalmometer (UDT Sensor, Inc, Hawthorne, CA) with a calibrated silicon photodiode (UDT Sensor, Inc, Hawthorne, CA). Unless otherwise specified, all tests were performed at approximately 20 ° C room temperature.

达較性試驗A 該比較性試驗說明在形成緩衝層以試圖製造發光二極體時得到的結果’該緩衝層藉由將一種不具界面活性劑之水-性聚苯胺分散液旋塗於含氧化錫銦（ΙΊΌ)陽極之柔韌性基材上形成。Comparability test A This comparative test illustrates the results obtained when a buffer layer was formed in an attempt to make a light-emitting diode. 'The buffer layer was prepared by spin-coating a water-based polyaniline dispersion without a surfactant on an oxidation-containing polyaniline. Formed on a flexible substrate of a tin indium (II) anode.

在此比較性試驗中使用的柔韌性基材為〇C50/ST5〇4 PET 200304238 在其一侧上 (η) 7-密耳（mil)( 180微米）聚（對酞酸乙二醇醋）片，且已沈積50歐姆/平方(〇hm/square)ITO薄層，白t 曰薄膜公司獲得 (Canoga Park ; CA)。將具有ITO層之6英寸y !尤1 /The flexible substrate used in this comparative test was OC50 / ST50 04 PET 200304238 on one side (η) 7-mil (mil) (180 microns) poly (ethylene terephthalate) Sheet, and a thin layer of 50 ohm / square (0hm / square) ITO has been deposited, available from Thin Film Corporation (Canoga Park; CA). Will have 6 inches of ITO layer! Especially 1 /

丁 X 1奂寸（15.2釐米X 2.5釐：米）PET片切成1英寸（2.5爱米）方塊。然後將此等方塊用以下方式淨化及乾燥。自无在聲處理浴中用自埃侖公司（Alonox，Inc)的 Liqu卜Nox® (New Y〇rk Νγ) 之稀去離子水溶液淨化1小時。將方塊置於支架上，然後用去離子水清洗。將它們放入具有新鮮去離子水的聲處理浴，且再次聲處理1小時。然後自支架移除方塊，且首先單_ 獨用去離子水清洗，然後用異丙醇清洗。然後將方塊再置於支架上，將支架放入室溫（約20°C )真空烘箱過夜。旋塗水性聚苯胺分散液如下進行。將顯微鏡載片放在裝配於自海威研究公司（Headway Research Inc·)(德克薩斯州，％藍）（Gadand，Texas)旋塗器的夾盤上。將細水滴置於載片中心，以在置於載片上時將方塊保持在適合位置。具有IT〇層 4方塊表面向上，且在此ΙΤΟ層上放置水性聚苯胺分散液。水性聚苯胺分散液為Ormecon® D1002W，該分散液包含於水中的2.6重量％聚苯胺，自〇rmecon chemie Gmbh & Co, KG獲得 (Aammersbek，Germany)。為將苯胺旋塗於方塊的ITO層上，將分散液吸在方塊上，以覆蓋其表面，而後以2,500轉/分鐘旋轉夾盤60秒鐘。在旋轉停止時，沒有在方塊上沈積的聚苯-胺痕。這說明，在不使用界面活性劑時，在具有ΙΤΟ塗層之柔韌性基材上沈積聚苯胺困難。實例1 -15 - (12) (12)200304238Ding X 1 奂 inch (15.2 cm X 2.5 centimeters: m) PET flakes cut into 1 inch (2.5 mm) cubes. These blocks are then purified and dried in the following manner. The sonication bath was cleaned with a dilute deionized aqueous solution of Liqub Nox® (New York Nγ) from Alonox, Inc. for 1 hour. Place the cube on the stand and wash it with deionized water. They were placed in a sonication bath with fresh deionized water and sonicated again for 1 hour. Then remove the cube from the stand, and clean it with deionized water alone and then with isopropyl alcohol. Then place the cube on the stand and place the stand in a vacuum oven at room temperature (about 20 ° C) overnight. The spin coating of the aqueous polyaniline dispersion was performed as follows. The microscope slide was placed on a chuck mounted on a spinner from Headway Research Inc. (Gadand, Texas). Place a droplet of water in the center of the slide to hold the cube in place when placed on the slide. It has an IT0 layer. 4 The surface of the square is upward, and an aqueous polyaniline dispersion is placed on this IT0 layer. The aqueous polyaniline dispersion was Ormecon® D1002W. This dispersion contained 2.6% by weight of polyaniline in water and was obtained from Ormecon chemie Gmbh & Co, KG (Aammersbek, Germany). To spin-coat the aniline onto the square ITO layer, the dispersion was sucked onto the square to cover its surface, and then the chuck was rotated at 2,500 rpm for 60 seconds. When the rotation was stopped, there were no polyphenylamine traces deposited on the block. This shows that it is difficult to deposit polyaniline on a flexible substrate with an ITO coating without using a surfactant. Example 1 -15-(12) (12) 200304238

本實例證明用含緩衝層之發光二極體得到的結果，該緩衝層藉由將一種已加入聚氧伸乙基（10)異辛基苯基醚界面活性劑 < 水性聚苯胺分散液旋塗於含ITO陽極之柔韌性基材上而形成。將對照試驗1中淨化和乾燥的具有IT〇層之柔韌性pET基材方塊用於旋塗水性聚苯胺分散液以11^〇1^〇1〇〇2^¥(2.6重量％於水中的聚苯胺），該分散液已加入丁riton® X-100聚氧伸乙基（10)異辛基苯基醚，一種非離子性界面活性劑[產品# 234729，美國，密蘇裏州，聖·路易斯，西格馬-阿瑞公司- (Sigma-Alddch Corp·，St· Louis，MO, USA)]。Triton® Χ·1〇〇之濃度為在 Ormecon D1002W 中的〇.35重量％Triton® X-100。旋塗含界面活性劑之水性分散液以基本上與比較性試驗A所述相同之方式進行。結果為在ITO層上的導電聚苯胺和界面活性劑之光/骨·塗層。將經塗覆IT0-PET方塊置於真空烘箱中，塗層在室溫乾燥過夜，而後在2,500轉/分鐘用1.5〇重量％於對二甲表中的聚芴旋塗60秒。聚芴（一種綠色發射物質）為gb〇〇1 (Cambridge Display Technology，Cambridge，UK)並作為活性發射層。將經塗覆樣品置於室溫真空烘箱中過夜，而後蒸氣沈積陰極，一具有1.0毫米直徑和約200奈米厚之鋁點陣列。這冗成發光二極體之製造。如上述對這一柔韌性發光二極體進行發光檢測。在裝置-電壓和電流分別為5.3伏特和1毫安培時，該裝置具有3 5伏特之接通電壓和320奈安培之光電二極體電流。當光電二極體電流僅為100奈安培時，在室光下發光顯然明亮。本實例 -16 - 200304238This example demonstrates the results obtained with a light-emitting diode containing a buffer layer by spinning a polyoxyethylene (10) isooctylphenyl ether surfactant < aqueous polyaniline dispersion It is formed by coating on a flexible substrate containing an ITO anode. The cleaned and dried flexible pET substrate with IT0 layer in Control Test 1 was used to spin-coat an aqueous polyaniline dispersion at 11 ^ 〇1 ^ 〇1〇〇2 ^ (2.6% by weight of polymer in water). Aniline), this dispersion has been added with butyl riton® X-100 polyoxyethylene (10) isooctylphenyl ether, a nonionic surfactant [Product # 234729, USA, Missouri, St. · Louis, Sigma-Are Corporation-(Sigma-Alddch Corp., St. Louis, MO, USA)]. The concentration of Triton® X · 100 is 0.35% by weight Triton® X-100 in Ormecon D1002W. Spin-coating an aqueous dispersion containing a surfactant was performed in substantially the same manner as described in Comparative Test A. The result was a light / bone · coating of conductive polyaniline and surfactant on the ITO layer. The coated ITO-PET cube was placed in a vacuum oven, and the coating was dried at room temperature overnight, and then spin-coated with 1.50% by weight of polyfluorene in parylene for 60 seconds at 2,500 rpm. Polyfluorene (a green emitting substance) is gb001 (Cambridge Display Technology, Cambridge, UK) and serves as an active emitting layer. The coated samples were placed in a room temperature vacuum oven overnight, and then a cathode was vapor deposited, an array of aluminum dots having a diameter of 1.0 mm and a thickness of about 200 nm. This is redundant to the manufacture of light emitting diodes. Luminescence detection was performed on this flexible light-emitting diode as described above. When the device-voltage and current are 5.3 volts and 1 milliamp, respectively, the device has an on-voltage of 35 volts and a photodiode current of 320 nanoamperes. When the photodiode current is only 100 nanoamperes, the luminescence is clearly bright under room light. This example -16-200304238

說明用已加入界面活性劑聚氧伸乙基（ίο)異辛基苯基醚的導電聚合物聚苯胺之水性聚苯胺分散液形成緩衝層以及該緩衝層在柔韌性基材上用於聚合性發光二極體之性能。此結果與比較性試驗A之比較顯示存在界面活性劑之優點。Description A buffer layer is formed by using an aqueous polyaniline dispersion of a conductive polymer polyaniline to which a surfactant polyoxyethylene (ison) isooctylphenyl ether has been added, and the buffer layer is used for polymerizability on a flexible substrate. Performance of light-emitting diodes. A comparison of this result with Comparative Experiment A shows the advantage of the presence of a surfactant.

比較性試驗BComparative test B

該比較性試驗說明在形成緩衝層以試圖製造發光二極體時得到的結果，該緩衝層藉由將一種不具界面活性劑之水性聚苯胺分散液旋塗於含ITO陽極之柔韌性基材上形成。This comparative test illustrates the results obtained when forming a buffer layer in an attempt to manufacture a light emitting diode, which is prepared by spin coating an aqueous polyaniline dispersion without a surfactant onto a flexible substrate containing an ITO anode form.

在此比較性試驗中使用的柔韌性基材為Alt-0-25-B-G-7_ (180微米）聚（對酞酸乙二醇酯）PET片，在其一侧已沈積25歐姆/平方ITO薄層，自南井技術公司獲得（Southwall Technologies, Inc·) (Palo Alto，CA)。用基本與比較性試驗 A中所述相同之方法將自片切成的1英寸（2.5釐米）方片淨化及乾燥。旋塗水性聚苯胺分散液Ormecon® D1002W (2.6重量％於水中的聚苯胺）用基本與比較性試驗A中所述相同之方法進行。水性分散液在基材上形成高接觸角，因此在IT0表面僅得到斑點狀覆蓋。由於聚苯胺斑點狀塗覆，用電冷光聚合物溶液旋塗表面形成陰極及完成發光二極體不能進行。實例2 本實例說明用一含緩衝層之發光二極體得到的結果，該緩衝層藉由將一種已加入聚氧伸乙基（10)異辛基苯基醚界面活性劑之水性聚苯胺分散液旋塗於含ITO陽極之柔韌性基材上形成。The flexible substrate used in this comparative test was Alt-0-25-BG-7_ (180 microns) poly (ethylene terephthalate) PET sheet with 25 ohm / square ITO deposited on one side Thin layer, obtained from Southwall Technologies, Inc. (Palo Alto, CA). A 1-inch (2.5 cm) square piece cut from the sheet was purified and dried in the same manner as described in Comparative Test A. Spin-coating an aqueous polyaniline dispersion Ormecon® D1002W (2.6% by weight polyaniline in water) was performed in substantially the same manner as described in Comparative Test A. The aqueous dispersion forms a high contact angle on the substrate, so only a spot-like coverage is obtained on the surface of IT0. Due to the spot coating of polyaniline, spin-coating the surface with an electroluminescent polymer solution to form a cathode and complete a light-emitting diode cannot be performed. Example 2 This example illustrates the results obtained with a light-emitting diode containing a buffer layer by dispersing an aqueous polyaniline to which a polyoxyethylene (10) isooctylphenyl ether surfactant has been added. Spin-coated on a flexible substrate containing an ITO anode.

將比較性試驗B中淨化和乾燥的具有ITO層之柔韌性PET -17 - 200304238 (14) 基材方塊用於旋塗水性聚苯胺分散液〇rmec〇n® D1002W (2.6 重量％於水中的聚苯胺），該分散液已加入Triton® X-100，聚氧件乙基（10)異辛基苯基醚。Trit〇n® χ·1〇〇之濃度為在The flexible PET -17 with a ITO layer purified and dried in Comparative Test B was used to spin-coat an aqueous polyaniline dispersion, rmecon® D1002W (2.6% by weight of polymer in water). Aniline), this dispersion has been added to Triton® X-100, polyoxyethyl (10) isooctylphenyl ether. The concentration of Trit〇n® χ · 100 is

Ormecon® D1002W中的〇 4〇重量％Triton® Χ-100。旋塗含界面0.4% by weight Triton® X-100 in Ormecon® D1002W. Spin coating with interface

活性劑之水性分散液以基本上與比較性試驗A中所述相同之方式進行。結果為在IT0層上的導電聚苯胺和界面活性劑之光滑塗層。按照實例丨之步驟完成發光二極體之製造。對該發光二極體進行發光檢測基本如實例1中所述。在裝置電壓和電流分別為6.6伏特和1毫安培時，該裝置具有4 〇伏特-之接通電壓和241奈安培之光電二極體電流。當光電二極體電流僅為1〇〇奈安培時，在室光下發光顯然明亮。本實例說明用已加入界面活性劑聚氧伸乙基（1〇)異辛基苯基醚的導電聚合物聚苯胺之水性分散液形成緩衝層以及該緩衝層在柔韌性基材上用於聚合性發光二極體之性能。此結果與比較性試驗B之比較顯示存在界面活性劑之優點。The aqueous dispersion of the active agent was performed in substantially the same manner as described in Comparative Test A. The result is a smooth coating of conductive polyaniline and surfactant on the ITO layer. The manufacturing of the light emitting diode is completed according to the steps of Example 丨. The light-emitting detection of the light-emitting diode is basically as described in Example 1. When the device voltage and current were 6.6 volts and 1 milliamp, respectively, the device had an on-voltage of 40 volts and a photodiode current of 241 nanoamperes. When the photodiode current is only 100 nanoamperes, the luminescence is clearly bright under room light. This example illustrates the formation of a buffer layer using an aqueous dispersion of a conductive polymer polyaniline to which a surfactant polyoxyethylene (10) isooctylphenyl ether has been added, and the buffer layer is used for polymerization on a flexible substrate Performance of sexual light-emitting diodes. Comparison of this result with Comparative Test B shows the advantage of the presence of a surfactant.

實例3-5和比較性試驗實例3-5說明用—含缓衝層之pLEDs得到的結果，該緩衝層藉由將-種已加人不同量聚氧伸乙基⑽異辛基苯基醜界面活性劑之水性聚苯胺分散液旋塗於含ιτ〇陽極之柔韌性基材上形成。比較性試驗C說明用一不含緩衝層之發光二極體得到的結果。比較性試驗D說明用—含緩衝層之發光二極體得到的結I，該緩衝層藉由將一種不具有界面活性劑的水性聚苯胺分散液旋塗於含陽極之柔韌性基材上形成。用於此等實例和比較性試驗的柔韌性基材為 -18 - 200304238Examples 3-5 and Comparative Test Examples 3-5 illustrate the results obtained using pLEDs with a buffer layer by adding a different amount of polyoxyethylene ethyl isooctylphenyl Aqueous polyaniline dispersion of surfactant is spin-coated on a flexible substrate containing ιτ〇 anode. Comparative test C illustrates the results obtained with a light-emitting diode without a buffer layer. Comparative test D illustrates junction I obtained with a light-emitting diode with a buffer layer formed by spin coating an aqueous polyaniline dispersion without a surfactant on a flexible substrate containing an anode . Flexible substrates used in these examples and comparative tests are -18-200304238

(15) NV1-062/ST504 5-密耳（π〇微米）聚（對S太酸乙二醇酯）（PET) 片，在其一側已沈積40歐姆/平方ITO薄層，自NeoVac獲得 (Santa Rosa，CA)。用基本與比較性試驗A中所述相同之方法淨化和乾燥1英寸方片 .............. ，性聚苯胺分散液為〇rmec〇n® D1002W，2.6重量％於水中的聚苯胺。用於比較性試驗D之緩衝層的分散液不含界面活性劑。用於旋塗實例3、4和5之緩衝層的分散液分別具有在(15) NV1-062 / ST504 5-mil (π micron) poly (p-S-ethylene glycol) (PET) sheet, with a 40 ohm / square ITO thin layer deposited on one side, obtained from NeoVac (Santa Rosa, CA). Purify and dry a 1-inch square piece by the same method as described in Comparative Test A ............. The polyaniline dispersion is omcoon® D1002W, 2.6 weight % Polyaniline in water. The dispersion of the buffer layer used in Comparative Test D contained no surfactant. The dispersions for the spin-coating buffer layers of Examples 3, 4, and 5 have

Ormecon ⑧ D1002W 中的〇〇5、〇·ι 和〇 35 重量。/〇Triton ⑧ X-100 聚氧伸乙基（10)井辛基苯基醚界面活性劑之濃度。旋塗含界面活生鈉及典界面活性劑之水性分散液用基本與比較性試驗A 中所述相同〈方式進行。按照實例k步騾完成發光二極體 ^製造。用於比較性試驗c的方塊不含緩衝層，所以旋塗聚勿層直接於IΤ Ο層上i隹；。么田r、< 、丁 ”、、界面活性劑的聚苯胺分散液未在比較性試驗D中充分渴、、問本主 ^ 刀濕'閏表面’以致不能提供完全、光滑表面覆盖’而因此得到斑點 ^ ^ ^ ^ - i7 ^ 、^勾缓衝層。但在試圖 I k發光一極體中沈積活005, 〇 · ι and 〇 35 weights in Ormecon (R) D1002W. / 〇 Triton ⑧ X-100 polyoxyethylene (10) well octyl phenyl ether surfactant concentration. Spin-coating an aqueous dispersion containing interfacial sodium and a typical surfactant was performed in substantially the same manner as described in Comparative Test A. Follow the example k steps to complete the fabrication of the light emitting diode. The square used for the comparative test c does not contain a buffer layer, so the spin-coated polymer layer is directly on the ITO layer. Modian R, <, D, ", polyaniline dispersion of surfactant, not sufficiently thirsty in comparative test D, asked the subject ^ knife wet '湿 surface' so as not to provide complete, smooth surface coverage ' So get the spots ^ ^ ^ ^-i7 ^, ^ tick buffer layer. But trying to deposit live

散射層和鋁點陰極。發光檢測如上述進行，处丁、，告果顯不於表1中。 -19- (16) 200304238 表1 /、、、緩衝層接通電壓光電二極體電流裝置電壓(伏特）比較性試驗品質 (伏特）（微安） @1毫安培裝置電流比較性試驗c無緩衝層 55 比較性試驗D 不均句 4 〇實例3 均勻 4.0 實例4 均勻 3 5 實例5 均勾 4〇一培裝置電流 0.62 10.5 1.07, 0·72 5.8, 8.2 °·90 5.6 110 5.6 0.66 5.5 · 不具緩衝層的比較性試驗匸之PLED比具緩衝層的比較性減發#只％ 3_5者具有較高接通電壓及工作電壓。對於比車义4 D的表丨中所示數據為兩個陰極點之結果。一個在裝置私壓和私成分別為5·8伏特和1毫安培時具有1 ·07微安之光％極缸見成。而另一個在裝置電壓和電流分別為8.2伏特彳1毛安圪時具有〇 72微安之光電二極體電流。該可變性為不使用界面活从+ ϊ l / #座劑時緩衝層的不均勻性之結果。實例3-5Scattering layer and aluminum dot cathode. Luminescence detection was performed as described above, and the results were not shown in Table 1. -19- (16) 200304238 Table 1 / ,,, buffer layer turn-on voltage Photodiode current device voltage (volts) Comparative test quality (volts) (microampere) @ 1 milliampere device current comparative test c None Buffer layer 55 Comparative test D Heterogeneous sentence 4 〇 Example 3 Uniform 4.0 Example 4 Uniform 3 5 Example 5 Hook 4 〇 One culture device current 0.62 10.5 1.07, 0 · 72 5.8, 8.2 ° · 90 5.6 110 5.6 0.66 5.5 · Comparative test without buffer layer: The PLED has a higher on-voltage and operating voltage than the comparative reduction with the buffer layer. The data shown in Table 丨 for the car 4D is the result of two cathode points. A light-% pole cylinder with 1.07 microamperes at the device's private pressure and private components of 5.8 volts and 1 milliampere, respectively. The other has a photodiode current of 72 μA when the device voltage and current are 8.2 volts and 1 ampere. This variability is a result of the non-uniformity of the buffer layer when no interfacial active agent is used. Example 3-5

之PLEDs均比比赫从心A 性試驗C之PLED具有較低接通電壓、較高光電二極體電汸 w及較低工作電壓，且與比較性試驗D之 PLED對照自一個g k極點至另一個顯示一致性。隨著界面活性劑之量自實例3中千〇·〇5重量％水性分散液中的界面活性劑增加到實例4中〇；!舌田η/ 、 ! /ί>水性分散液中的界面活性劑，光電二極體電流增加，；此_ 、、 k奢界面活性劑之量增加到實例5中 0.3 5重量％水性分丧 /夜中的界面活性劑而降低α為在將聚氧伸乙基（10)異辛基笼1 y 恭本基醚界面活性劑加入此等實例的水性 -20- (17) (17)200304238 聚…散-時得到最大緩衝層性能改良，劑之量應為在水性分散液中至少0 05重量％界佳小於0.30重量。/。。 ^ 产兔复么绝此等實例和比較性試驗 j 、舉例說明必須加入水性聚苯胺分月文液的聚氧伸乙基（10)里辛厂、辛基丰基醚界面活性劑之量，以提供在柔韌性基材上產生 ^ p 陡此改艮的緩衝層塗覆能力所需之表面張力。用於此等實例和比較性4 ^ 改4 I的水性聚苯胺分散液為- OΓmecon® D1002W ， 2 6舌熹〇/ 、人 U 山 _ 重I /〇於水中的聚苯胺。比較性試驗 E只例6 - 8和比較性敍κλ. p ^ ' \ p 足为政液分別具有在〇rmecon® D1002W 中的 0.05、〇 1〇 ^ 16、0 5和 10重量％Triton® X-100[聚乳伸乙基(10)異辛基苯基醚]界面活性劑之濃度。如上所-述測量表面張力。比較性試驗E、i例6-8和比較性成驗# G之分散液之表面張力分別為Μ 9、Μ」、Μ > ^ 1·9及31.8¾牛頓/米。對於高於實例8濃度的界面活性劑濃度，Ρ卩，舌士人士， Ρ 问於在水性分散液中的〇.16重量％界面活性片面張力有很小變化。該水性分散液應使用的界面活性劑乏» » . t I為在水性分散液中至少約0·05重量％界面活性齊丨J ^ pt > ^ 在水性分散液中小於約0.40重量％界面活性劑，較佳在欠丨生分散液中小於約0.30重量％。較高濃度界面活性劑將不利於響裝置性能，如實例3_5和比較性試驗C_D中所示。例9-11和比較性試驗Η 此等實例和比較性試驗舉例說明必須加入水性聚（3,4-伸 -21 - 200304238All PLEDs have lower turn-on voltage, higher photodiode voltage, and lower operating voltage than the PLEDs of Bich from Heart A test C, and compare with the PLED of comparative test D from one gk pole to another One shows consistency. With the amount of surfactant in Example 3, the surfactant in the aqueous dispersion of 0.0005 wt% was increased to that in Example 4. 〇田田 η /,! / Ί > Interfacial activity in aqueous dispersion Agent, the photodiode current increased; the amount of this surfactant increased to 0.3% by weight of the surfactant in Example 5 and 5% by weight of the surfactant in the water while reducing α to increase the (10) Iso-octyl cage 1 y The methyl ether surfactant is added to these examples of water-based -20- (17) (17) 200304238 poly ... scattered-when the maximum buffer layer performance is improved, the amount of agent should be at At least 0.05% by weight of the aqueous dispersion is preferably less than 0.30% by weight. /. . ^ These examples and comparative tests are used to give birth to rabbits, and to illustrate the amount of polyoxyethylene (10) Lixin plant and octylfengyl ether surfactant that must be added to aqueous polyaniline liquid. In order to provide the surface tension required to produce a coating layer on the flexible substrate. The aqueous polyaniline dispersion used in these examples and Comparative Example 4I was -Omeme® D1002W, 26 6 〇 /, human U _ heavy I / 0 polyaniline in water. Comparative Test E only Examples 6-8 and Comparative Kappa λ. P ^ '\ p Zuo Wei Zheng Ye has 0.05, 〇〇〇〇〇 16, 16, 0 and 10% by weight Triton® X in Ormecon® D1002W, respectively -100 [Polylactenyl (10) isooctylphenyl ether] surfactant concentration. Surface tension was measured as described above. The surface tensions of the dispersions of Comparative Test E, Example 6-8 and Comparative Test #G were M 9, M ", M > ^ 1.9 and 31.8 ¾ Newton / meter, respectively. For the surfactant concentration higher than that of Example 8, PZ, tongues, and P have little change in the surface tension of 0.16% by weight of the interfacial activity in the aqueous dispersion. The surfactant used in the aqueous dispersion is depleted »». T I is at least about 0.05% by weight interfacial activity in the aqueous dispersion. J ^ pt > ^ less than about 0.40% by weight of the interface in the aqueous dispersion. The active agent is preferably less than about 0.30% by weight in the undergrowth dispersion. Higher concentrations of surfactant will be detrimental to device performance, as shown in Examples 3-5 and Comparative Test C_D. Examples 9-11 and comparative tests Η These examples and comparative tests illustrate the need to add water-based polymer (3,4-elongation -21-200304238

乙基二氧噻吩）/聚（苯乙烯磺酸酯（鹽））（PEDOT/PSS)分散液的聚氧伸乙基（10)異辛基苯基醚界面活性劑之量，以提供在柔韌性基材上產生性能改良的緩衝層塗覆能力所需之表面張力。用於此等實例和比較性試驗的水性PEDOT/PSS分散液為 Baytron®-P(VP AI4083)，自貝爾（Bayer)AG公司獲得（德國）。 Baytron®-P包含1.5至2.0重量％於水中的聚（3,4-伸乙基二氧嘧吩）/聚（苯乙烯磺酸酯（鹽））（PEDOT/PSS)。比較性試驗Η和實例 9-11之分散液分別具有在水性PEDOT/PSS分散液中的0、_ 0.05、0.10和0.15重量％Triton® Χ-100[聚氧伸乙基（1〇)異辛基苯基醚]界面活性劑之濃度。如上所堞測量表面張力。比較性試驗Η和實例9-11之分散液之表面張力分別為42.6、29.7、30.4和30.8毫牛頓/米。對於高於實例· 9濃度的界面活性劑濃度，即，高於在水性分散液中的0.05重量％界面活性劑，表面張力有很小變化。該水性分散液應使用的界面活性劑之量為在水性分散液中至少約 0.05重量％界面活性劑，且在水性分散液中小於約〇 4〇重量％界面活性劑，較佳在水性分散液中小於約〇.30重量％界面活性劑。實例和比較性試驗I，j 實例12 -16和比較性武驗I和J顯不用含緩衝層之p l E D s獲得的結果，該緩衝層藉由將已加入某些界面活性劑的水性聚苯胺/聚（2-丙烯驢胺基-2_甲基-l-丙績酸）（PAni/PAAMPSA) 分散液旋塗於含ITO陽極之玻璃基材上形成。 -22- 200304238Ethyldioxythiophene) / poly (styrene sulfonate (salt)) (PEDOT / PSS) dispersion in polyoxyethylene (10) isooctylphenyl ether surfactant amount to provide flexibility The surface tension required to produce a buffer layer with improved performance on a flexible substrate. The aqueous PEDOT / PSS dispersion used in these examples and comparative tests is Baytron®-P (VP AI4083), obtained from Bayer AG (Germany). Baytron®-P contains 1.5 to 2.0% by weight of poly (3,4-ethylenedioxypyrimidine) / poly (styrenesulfonate (salt)) (PEDOT / PSS) in water. The dispersions of Comparative Test Η and Examples 9-11 have 0, _0.05, 0.10, and 0.15% by weight of Triton® X-100 [polyoxyethylene (1)) isooctene in aqueous PEDOT / PSS dispersions, respectively. Phenyl ether] surfactant concentration. Measure the surface tension as described above. The surface tensions of the dispersions of Comparative Test VII and Examples 9-11 were 42.6, 29.7, 30.4, and 30.8 mN / m, respectively. For a surfactant concentration higher than that of Example 9, that is, higher than 0.05% by weight of the surfactant in the aqueous dispersion, there was a small change in surface tension. The amount of the surfactant to be used in the aqueous dispersion is at least about 0.05% by weight of the surfactant in the aqueous dispersion, and less than about 0.40% by weight of the surfactant in the aqueous dispersion, preferably in the aqueous dispersion. In less than about 0.30% by weight of surfactant. Examples and comparative tests I, j Examples 12-16 and comparative tests I and J show results obtained without pl ED s containing a buffer layer by adding aqueous polyaniline to which certain surfactants have been added / Poly (2-acrylamido-2-methyl-l-propionic acid) (PAni / PAAMPSA) dispersion was formed by spin coating on a glass substrate containing an ITO anode. -22- 200304238

(19) 玻璃基材為3董米X3董米，且具有具loo至15〇奈米厚度之 1.5釐米X 2.0釐米ΐτο層。用基本與比較性試驗a中所述相同之方法將此等具有ITO層之基材淨化及乾燥，隨後用氧電漿處理，以有目的去除濕潤性因素，用於比較具有不同界面活性劑的發光性能。(19) The glass substrate is 3 Dongm X 3 Dongm, and has a layer of 1.5 cm X 2.0 cm ΐτο with a thickness of loo to 150 nm. These substrates with an ITO layer were purified and dried in the same manner as described in the comparative test a, and then treated with an oxygen plasma to purposefully remove the wettability factor for comparison of different surfactants. Luminous performance.

用於旋塗緩衝層的水性分散液為1 〇重量％在水中的導電性聚苯胺/聚（2-丙稀·醯胺基-2-甲基-1-丙橫酸）pAni/P (AAMPSA) ’ 自尤尼公司（Uniax Corp·)獲得（Santa Barbara，CA)。沒有界面活性劑加入用於旋塗比較性試驗I之緩衝層之-水性分散液。加入用於旋塗比較性試驗j緩衝層的水性分散液之界面活性劑為十二燒基硫酸經，一種離子性界面活性劑（分類#86，190-1，美國，密蘇裏州，聖·路易斯，西格馬阿瑞公司）。十二烷基硫酸鋰之濃度為在水性pAni/p (AAMPSA)分散液中〇.15重量％十二烷基硫酸鋰。加入用於旋塗實例12緩衝層的水性分散液之界面活性劑為Trit〇n® X-100[聚氧伸乙基（10)異辛基苯基醚]。Trit〇n® H〇〇之濃度為在水性PAni/P (AAMPSA)分散液中0.15重量％Triton® X-100。加入用於旋塗實例13緩衝層的水性分散液之界面活性劑為Zonyl® FS-300，一種包含全氟烷基聚氧伸乙基之非離子性界面活性劑，其具式RfCH2CH20(CH2CH20)zH，其中Rf 為具有式F(CF2CF2)3_8之全氟燒基[德拉瓦州，維明頓，杜邦-公司（Dupont Co·，Wilmington，DE)]。Zonyl⑧ FS-300之濃度為在水性 PAni/P (AAMPSA)分散液中 0.15重量％Zonyl® FS-300。加入用於旋塗實例14緩衝層的水性分散液之界面活性劑為 -23 - 200304238Aqueous dispersion for spin-coating buffer layer is 10% by weight of conductive polyaniline / poly (2-propyl · amido-2-methyl-1-propanoic acid) pAni / P (AAMPSA ) 'Acquired from Uniax Corp. (Santa Barbara, CA). No surfactant was added to the aqueous dispersion of the buffer layer used for spin-coating Comparative Test I. The surfactant added to the aqueous dispersion for the spin-coating comparative test was a dodecyl sulfate, an ionic surfactant (class # 86,190-1, USA, Missouri, St. · Louis, Sigma Inc.). The concentration of lithium dodecyl sulfate was 0.15% by weight of lithium dodecyl sulfate in an aqueous pAni / p (AAMPSA) dispersion. The surfactant added to the aqueous dispersion for spin coating of the buffer layer of Example 12 was Triton® X-100 [polyoxyethyl (10) isooctylphenyl ether]. The concentration of Triton® H〇〇 is 0.15% by weight of Triton® X-100 in an aqueous PAni / P (AAMPSA) dispersion. The surfactant added to the aqueous dispersion for spin coating of the buffer layer of Example 13 is Zonyl® FS-300, a non-ionic surfactant containing perfluoroalkyl polyoxyethylene, which has the formula RfCH2CH20 (CH2CH20) zH, where Rf is a perfluorocarbon group having the formula F (CF2CF2) 3-8 [Delaware, Wilmington, Dupont Co., Wilmington, DE]. The concentration of Zonyl (R) FS-300 is 0.15% by weight of Zonyl® FS-300 in an aqueous PAni / P (AAMPSA) dispersion. The surfactant added to the aqueous dispersion for spin coating of the buffer layer of Example 14 is -23-200304238

ZonyP FSN-100，一種包含全氟烷基聚氧伸乙基之非離子性界面活性劑，其具式RfCH2CH20(CH2CH20)xH，其中Rf為具有式F(CF2CF2)3_8之全氟烷基（德拉瓦州，維明頓，杜邦公司）。 Zonyl® FSN-100之濃度為在水性PAni/P (AAMPSA)分散液中 0.15重量％Zonyl® FSN-100。加入用於旋塗實例15緩衝層的水性分散液之界面活性劑為3M® Fluorad⑧氟界面活性劑 FC-430，一種含氟脂系聚合酯之非離子性含氟界面活性劑 (3M，St· Paul·，MN)。FC-430之濃度為在水性 PAni/P (AAMPSA) 分散液中〇.〇5重量％FC-430。加入用於旋塗實例16緩衝層的水性分散液之界面活性劑為Zonyl® FSA，一種包含全氟烷基伸乙基硫伸乙基的碳酸經鹽之離子性氟界面活性劑，其具式 RfCH2CH2SCH2CH2C02Li，其中 Rf為具有式 F(CF2CF2)3.8i 全氟烷基[德拉瓦州，維明頓，E. I·杜邦耐默斯公司（E.I. duZonyP FSN-100, a non-ionic surfactant containing a perfluoroalkyl polyoxyethyl group, has the formula RfCH2CH20 (CH2CH20) xH, where Rf is a perfluoroalkyl group having the formula F (CF2CF2) 3_8 Lava, Wilmington, DuPont). The concentration of Zonyl® FSN-100 is 0.15% by weight of Zonyl® FSN-100 in an aqueous PAni / P (AAMPSA) dispersion. The surfactant added to the aqueous dispersion for spin coating of the buffer layer of Example 15 is 3M® Fluorad (fluorine surfactant) FC-430, a non-ionic fluorine-containing surfactant (3M, St. Paul ·, MN). The concentration of FC-430 is 0.05-5% by weight of FC-430 in an aqueous PAni / P (AAMPSA) dispersion. The surfactant added to the aqueous dispersion for spin coating of the buffer layer of Example 16 is Zonyl® FSA, an ionic fluorosurfactant containing perfluoroalkyl and ethyl thioethenyl carbonate via salt. , Where Rf is a perfluoroalkyl group having the formula F (CF2CF2) 3.8i [Delaware, Wilmington, E.I. DuPont Naimers (EI du

Pont de Nemours and Company，Wilmington，DE)]。該 Zonyl® FSA 之濃度為在水性PAni/P (AAMPSA)分散液中o.io重量。/〇Zonyl® FSA。將具或不具界面活性劑的各水性分散液在1200轉/分鐘之旋轉速度旋塗於含ITO之玻璃基材上。緩衝層厚度在50奈米之範圍内；各厚度顯示於表II中。將具緩衝層的含ITO玻璃基材在90°C氮氣中乾燥30分鐘。然後以基本與對旋塗實例1活性發射層所述相同之方式-用活性發射層旋塗緩衝層，該發射層由黃色發射劑PDY® 13 1 聚（經取代伸冬基伸乙缔基）（Covion Company，Frankfurt， Germany)組成。活性發射層之厚度接近70奈米。所有薄膜厚 -24 - 200304238Pont de Nemours and Company, Wilmington, DE)]. The concentration of Zonyl® FSA is o.io weight in aqueous PAni / P (AAMPSA) dispersion. / 〇Zonyl® FSA. Each aqueous dispersion with or without a surfactant was spin-coated on a glass substrate containing ITO at a rotation speed of 1200 rpm. The thickness of the buffer layer is in the range of 50 nm; each thickness is shown in Table II. The buffered ITO-containing glass substrate was dried under nitrogen at 90 ° C for 30 minutes. The buffer layer was then spin-coated with an active emissive layer, essentially the same as described for spin-coating the active emissive layer of Example 1, which was replaced by the yellow emissive agent PDY® 13 1 (substituted butylene and ethylene) Covion Company, Frankfurt, Germany). The thickness of the active emission layer is close to 70 nm. All film thickness -24-200304238

度用 TENCOR 500 表面光度儀測量（TENCOR，Inc.，Mountain View，CA) 〇為作為各PLEDs的陰極，在1 X 1(Γό托（tor〇真空下首先使鋇層然後使鋁層蒸氣沈積於活性發射層頂上。鋇層厚度為3 奈米；銘層厚度為300奈米。如上述檢測裝置性能，結果顯示於表II中。表II 實例或緩衝層電壓(伏特）效率亮度比較性試驗 @200坎德拉/米2 (坎德拉/安培） (坎德拉/米2) _ 厚度亮度 @200坎德拉/米2 @3.3毫安培/釐米2， (奈米）亮度 80°C 比較性試驗I 59.8 3.3 6.7 204 比較性試驗J ‘ 44.0 電短路 - - 實例12 48.7 3.2 7.6 234 實例13 - 44.6 3.2 7.6 240 實例14 57.4 3.2 8.0 200 實例15 52.4 3.5 7.5 - 實例16 47.8 3.2 7.2 - 比較性試驗J之緩衝層中所用的十二烷基硫酸鋰界面活性劑導致PLED中電短路，表明烷基硫酸鹽界面活性劑不應用於製造緩衝層。實例12之PLED具有用加入水性PAni/P (AAMPSA)分散液的聚氧伸乙基（10)異辛基苯基醚界面活性劑製造的緩衝層，與具有無界面活性劑加入水性PAni/P (AAMPSA)分散液製造的緩衝層之比較性試驗I之PLED比較，實例12之PLED顯示在 200坎德拉/米2的較高發光效率、在200坎德拉/米2的可比較 -25 - 200304238The degree of measurement was measured with a TENCOR 500 surface photometer (TENCOR, Inc., Mountain View, CA). As a cathode of each PLEDs, a barium layer was firstly deposited under a vacuum of 1 × 1 (Γό Torr) and then an aluminum layer was deposited on On top of the active emission layer. The thickness of the barium layer is 3 nm; the thickness of the Ming layer is 300 nm. The performance of the above detection device is shown in Table II. Table II Examples or buffer layer voltage (volts) Efficiency and brightness comparison test @ 200 candela / m2 (candela / amp) (candela / m2) _ thickness brightness @ 200 candela / m2 @ 3.3 milliamps / cm2, (nano) brightness 80 ° C comparative test I 59.8 3.3 6.7 204 comparison Test J '44.0 Electrical short--Example 12 48.7 3.2 7.6 234 Example 13-44.6 3.2 7.6 240 Example 14 57.4 3.2 8.0 200 Example 15 52.4 3.5 7.5-Example 16 47.8 3.2 7.2-Used in the buffer layer of Comparative Test J The lithium dodecyl sulfate surfactant caused an electrical short circuit in the PLED, indicating that the alkyl sulfate surfactant should not be used in the manufacture of the buffer layer. The PLED of Example 12 has polyoxygen added with aqueous PAni / P (AAMPSA) dispersion Comparison of a buffer layer made of ethyl (10) isooctylphenyl ether surfactant with a PLED in comparative test I with a buffer layer made of an aqueous PAni / P (AAMPSA) dispersion without surfactant, Example 12 PLED shows higher luminous efficiency at 200 candela / m2, comparable at 200 candela / m2 -25-200304238

接通電壓以及在3.3毫安培/釐米2和80°C的較高發光亮度。實例13-16之PLEDs具有用加入水性ΡΑη"Ρ (AAMPSA)分散液的含氟界面活性劑製造之缓衝層’與具有無界面活性劑加入水性PAni/P (AAMPSA)分散液製造的缓衝層之比較性試驗I之PLED比較，實例13-16之PLED顯示在200坎德拉/米2的較高發光效率、在200坎德拉/米2的略低或可比較接通電壓以及在3.3毫安培/爱米2和80°C的相當或較高發光亮度。此等實例和比較性試驗說明用含緩衝層之PLEDs得到的 PLED性能改良，該緩衝層藉由旋塗水性聚苯胺/聚（2_丙烯醯^ 胺基-2-甲基-1-丙續酸）分散液形成，且該分散液已加入聚氧伸乙基（10)異辛基苯基醚界面活性劑、包括氟脂系聚合酯的含氟界面活性劑或包含具式F(CF2CF2)3-8之全氟烷基之含氟界面活性劑。Switch-on voltage and higher luminous brightness at 3.3 mA / cm2 and 80 ° C. The PLEDs of Examples 13-16 have a buffer layer made of a fluorosurfactant with an aqueous PAN " P (AAMPSA) dispersion and a buffer made with an surfactant-free aqueous PAni / P (AAMPSA) dispersion Comparison of the PLEDs of the layer I comparative test I, the PLEDs of Examples 13-16 show higher luminous efficiency at 200 candela / m2, slightly lower or comparable on-voltage at 200 candela / m2, and at 3.3 mA / Equivalent or higher luminous brightness of Imi 2 and 80 ° C. These examples and comparative tests demonstrate the improved PLED performance obtained with PLEDs containing a buffer layer that is spin-coated with water-based polyaniline / poly (2-acryl-2-amino-1-methyl-1-propane) Acid) dispersion, and the dispersion has been added with polyoxyethylene (10) isooctylphenyl ether surfactant, a fluorosurfactant including a fluorolipid polymer ester, or containing formula F (CF2CF2) 3-8 perfluoroalkyl fluorinated surfactants.

實例17-20和比較性試驗K，L 實例17-20和比較性試驗K及L顯示用含緩衝層之PLEDs獲得的結果，該缓衝層藉由將已加入各種界面活性劑的水性聚（3,4-伸乙基二氧噻吩）/聚（苯乙烯磺酸酯（鹽》（pEDOT/PSS) 分散液旋塗於含ITO陽極之玻璃基材上形成。用於旋塗緩衝層的水性（PEDOT/PSS)分散液為 Baytron-P③，其包含1.5至2.0重量％於水中的聚（3,4-伸乙基二氧噻吩）/聚（苯乙烯磺酸酯（鹽））（PED0T/PSS)，且自貝爾AG公― 司（德國）獲得。沒有界面活性劑加入用於旋塗比較性試驗K之緩衝層之水性分散液。加入用於旋塗比較性試驗L緩衝層的水性分散 -26 - 200304238Examples 17-20 and Comparative Tests K, L Examples 17-20 and Comparative Tests K and L show the results obtained with PLEDs containing a buffer layer by adding aqueous poly ( 3,4-Ethylenedioxythiophene) / poly (styrene sulfonate (salt) (pEDOT / PSS) dispersion is spin-coated on a glass substrate containing an ITO anode. (PEDOT / PSS) dispersion is Baytron-P③, which contains 1.5 to 2.0% by weight of poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonate (salt)) (PEDOT / PSS), and obtained from Bell AG-Germany (Germany). No surfactant was added to the aqueous dispersion of the buffer layer for spin coating comparative test K. Aqueous dispersion for the spin coating of comparative buffer layer L was added -26-200304238

液之界面活性劑為十二烷基硫酸鋰。十二烷基硫酸鋰之濃度為在水性PEDOT/PSS分散液中0.15重量％十二烷基硫酸鋰。加入用於旋塗實例17緩衝層的水性分散液之界面活性劑為Triton® X-100，其濃度為在水性PEDOT/PSS分散液中0.15 重量％Triton⑧X-100。加入用於旋塗實例18緩衝層的水性分散液之界面活性劑為Zonyl® FS-300，其濃度為在水性 PEDOT/PSS分散液中0.15重量％Zonyl® FS-3 00。加入用於旋塗實例19緩衝層的水性分散液之界面活性劑為3M® Fluorad®氟界面活性劑FC-430，其濃度為在水性PEDOT/PSS分散液中_ 0.05重量％FC-430。加入用於旋塗實例20緩衝層的水性分散液之界面活性劑為Zonyl® FSA，其濃度為在水性PEDOT/PSS 分散液中〇.1〇重量％Zonyl® FSA。用與實例12-16中所述相同之基材和步騾製造發光二極體。裝置·如對實例12-16所述檢測，結果顯示於表III中。表III 實例或緩衝層電壓(伏特）效率亮度比較性試驗 @200坎德拉/米2 (坎德拉/安培） (坎德拉/米2) 厚度亮度 @200坎德拉/米2 @3.3毫安培/釐米2， (奈米）亮度 80°C 比較性試驗K 135 3.3 7.0 202 比較性試驗L 137 3.2 5.7 140 實例17 : 154 3.4 7.3 270 實例18 120 3.3 7.5 217 實例19 120 3.2 7.7 212 實例20 120 3.4 7.6 194 比較性試驗L之PLED具有用加入水性PEDOT/PSS分散液的 -27- 200304238The liquid surfactant is lithium dodecyl sulfate. The concentration of lithium dodecyl sulfate was 0.15% by weight of lithium dodecyl sulfate in an aqueous PEDOT / PSS dispersion. The surfactant added to the aqueous dispersion for spin coating of the buffer layer of Example 17 is Triton® X-100, which has a concentration of 0.15 wt% Triton (R) X-100 in an aqueous PEDOT / PSS dispersion. The surfactant added to the aqueous dispersion for spin coating of the buffer layer of Example 18 was Zonyl® FS-300, and its concentration was 0.15% by weight of Zonyl® FS-3 00 in the aqueous PEDOT / PSS dispersion. The surfactant added to the aqueous dispersion for spin coating of the buffer layer of Example 19 was 3M® Fluorad® fluorosurfactant FC-430 at a concentration of 0.05% by weight FC-430 in the aqueous PEDOT / PSS dispersion. The surfactant added to the aqueous dispersion for spin coating of the buffer layer of Example 20 was Zonyl® FSA, and its concentration was 0.10% by weight of Zonyl® FSA in the aqueous PEDOT / PSS dispersion. A light-emitting diode was manufactured using the same substrate and steps as described in Examples 12-16. Apparatus. Tests were performed as described in Examples 12-16, and the results are shown in Table III. Table III Example or buffer layer voltage (volts) Efficiency and brightness comparison test @ 200 candela / m2 (candela / amp) (candela / m2) Thickness brightness @ 200 candela / m2 @ 3.3 milliamps / cm2, (nai M) Brightness 80 ° C Comparative test K 135 3.3 7.0 202 Comparative test L 137 3.2 5.7 140 Example 17: 154 3.4 7.3 270 Example 18 120 3.3 3.3 7.5 217 Example 19 120 3.2 7.7 212 Example 20 120 3.4 7.6 194 Comparative test L's PLED has -27- 200304238 with the addition of aqueous PEDOT / PSS dispersion

十二垸基硫酸經界面活性劑製造之緩衝層，與具有無界面活性劑加入水性PEDOT/PSS分散液製造的緩衝層之比較性試驗K之PLED比較，比較性試驗L之PLED顯示在200坎德拉/ 米2的較低發光效率、在200坎德拉/米2的可比較接通電壓以及在3.3毫安培/釐米2和80°C的較低發光亮度。這再次說明，烷基硫酸鹽界面活性劑不應用於製造緩衝層。實例17之PLED具有用加入水性PEDOT/PSS分散液的聚氧伸乙基（10)異辛基苯基醚界面活性劑製造的緩衝層，與具有無界面活性劑加入水性PEDOT/PSS分散液製造的緩衝層之· 比較性試驗J之PLED比較，實例17之PLED顯示在200坎德拉/ 米2的較高發光效率、在200坎德拉/米2的可比較接通電壓以及在3.3毫安培/釐米2和80°C的較高發光亮度。實例18和20之PLEDs具有用加入水性PEDOT/PSS分散液的含氟界面·活性劑（包含具式F(CF2CF2)3_8之全氟烷基）製造的緩衝層，與具有無界面活性劑加入水性PEDOT/PSS分散液製造的緩衝層之比較性試驗K之PLED比較，實例18和20之PLED 顯示在200坎德拉/米2的較高發光效率、在200坎德拉/米2的可比較接通電壓以及在3.3毫安培/釐米2和80°C的較高或可比較發光亮度。實例19之PLED具有用加入水性PEDOT/PSS 分散液的含氟界面活性劑（包含氟脂系聚合酯）製造的緩衝層，與具有無界面活性劑加入水性PEDOT/PSS分散液製造的緩衝層之比較性試驗J之PLED比較，實例19之PLED顯示在 200坎德拉/米2的較高發光效率、在200坎德拉/米2的可比較接通電壓以及在3.3毫安培/釐米2和80°C的較高發光亮度。 -28 - 200304238Dodecyl sulphuric acid buffer layer made with surfactant, compared with PLED with comparative test K having buffer layer without surfactant added with aqueous PEDOT / PSS dispersion, PLED of comparative test L is shown at 200 candela Lower luminous efficiency per square meter, comparable turn-on voltage at 200 candela / square meter, and lower luminous brightness at 3.3 mA / cm2 and 80 ° C. This again illustrates that alkyl sulfate surfactants should not be used in the manufacture of buffer layers. The PLED of Example 17 has a buffer layer made of polyoxyethylene (10) isooctylphenyl ether surfactant added with an aqueous PEDOT / PSS dispersion, and made with a surfactant-free aqueous PEDOT / PSS dispersion. · Comparison of the PLED of the comparative test J, the PLED of Example 17 shows a higher luminous efficiency at 200 candelas / m2, a comparable on-voltage at 200 candelas / m2, and 3.3 mA / cm2 And higher luminous brightness of 80 ° C. The PLEDs of Examples 18 and 20 have a buffer layer made of a fluorine-containing interfacial active agent (including a perfluoroalkyl group having formula F (CF2CF2) 3_8) added with an aqueous PEDOT / PSS dispersion, and an aqueous solution with no interfacial active agent added. Comparative test of the PEDOT / PSS dispersion buffer layer test K for PLED comparison, the PLEDs of Examples 18 and 20 show higher luminous efficiency at 200 candela / m2, comparable on voltage at 200 candela / m2, Higher or comparable luminous brightness at 3.3 mA / cm2 and 80 ° C. The PLED of Example 19 has a buffer layer made of a fluorine-containing surfactant (including a fluorolipid-based polymer ester) added with an aqueous PEDOT / PSS dispersion, and a buffer layer made without a surfactant and added with an aqueous PEDOT / PSS dispersion. Comparison of the PLEDs of the comparative test J, the PLED of Example 19 showed higher luminous efficiency at 200 candela / m2, comparable on-voltage at 200 candela / m2, and 3.3 mA / cm2 and 80 ° C. Higher luminous brightness. -28-200304238

(25) 此等實例和比較性試驗說明用含緩衝層之PLEDs得到的改良結果’該緩衝層藉由旋塗水性聚（3，4-伸乙基二氧嚷吩）/ 聚（苯乙烯磺酸酯（鹽））分散液形成，且該分散液已加入聚氧伸乙基（10)異辛基苯基醚界面活性劑、包括氟脂系聚合酯的含氟界面活性劑或包含具式F(CF2CF:)3_8之全氟烷基之含氟界面活性劑。比較性試驗Μ 該比較性試驗說明在試圖於柔韌性基材上製造發光二極體時得到的結果，該發光二極體具有由金屬層和介電層組-成的雙層而無本發明之緩衝層。在此比較性試驗中使用的柔韌性基材為透明導電薄膜 Altair -Μ 1.0 (SouthWell Company，Palo Alto, CA) 7密耳（180微米）聚（對S太酸乙二醇酯）（PET)片。在該片一侧已先沈積一種介電層。由·能量分散χ_射線譜顯示為金/銀合金的金屬層已沈積於電介質上。氧化銦介電層已沈積於金屬層上。其具有 10歐姆/平方之片電阻。將具有雙層陽極之英寸XI英寸（305釐米X2.5釐米） PET片切成1英寸（2 5釐米）方塊。用基本與比較性試驗a中所述相同之方式淨化及乾燥此等方塊。按照實例1之步驟完成裝置之製造。具有電介質/金屬/電介質之基材表面向上，且旋轉8滴聚芴9〇秒。 _ 對孩發光二極體進行發光檢測基本如實例1中所述。如表 IV中所示忒裝置具有大於1 5伏特之接通電壓。當電壓增加问於15伏特時，在有發光象前鋁點陰極燒毀。該比較性 -29 - 200304238(25) These examples and comparative tests illustrate the improved results obtained with PLEDs containing a buffer layer. The buffer layer was spin-coated with water-soluble poly (3,4-ethylenedioxyphene) / poly (styrenesulfonate). Acid ester (salt)) dispersion liquid, and the dispersion liquid has been added with polyoxyethylene (10) isooctylphenyl ether surfactant, fluorine-containing surfactant including fluorolipid polymer ester, or F (CF2CF :) 3-8 perfluoroalkyl fluorosurfactant. Comparative test M This comparative test illustrates the results obtained when attempting to produce a light-emitting diode on a flexible substrate having a double layer composed of a metal layer and a dielectric layer without the present invention. Of the buffer layer. The flexible substrate used in this comparative test was a transparent conductive film Altair-M 1.0 (SouthWell Company, Palo Alto, CA) 7 mils (180 microns) poly (p-S-ethylene glycol) (PET) sheet. A dielectric layer has been deposited on one side of the sheet. From the energy dispersive χ-ray spectrum, it was shown that the metal layer of gold / silver alloy had been deposited on the dielectric. An indium oxide dielectric layer has been deposited on the metal layer. It has a sheet resistance of 10 ohms / square. An inch-by-inch (305 cm x 2.5 cm) PET sheet with a double anode was cut into 1 inch (25 cm) cubes. These blocks were purified and dried in substantially the same manner as described in Comparative Test a. The manufacturing of the device was completed according to the procedure of Example 1. The surface of the substrate with the dielectric / metal / dielectric is facing upward, and 8 drops of polyfluorene are rotated for 90 seconds. _ The detection of light emitting diodes is basically as described in Example 1. As shown in Table IV, the device has a turn-on voltage greater than 15 volts. When the voltage increase is about 15 volts, the aluminum dot cathode burns out before there is a glowing image. The comparison -29-200304238

(26) 試驗顯示’具有雙層陽極而無緩衝層之柔軔性基材不能產生發光二極體。(26) Tests have shown that a flexible substrate having a double-layer anode without a buffer layer cannot produce a light-emitting diode.

比較性試驗N 該比較性試驗說明在試圖於柔韌性基材上製造發光二極體時得到的結果，該發光二極體具有由金屬層和介電層組成的雙層陽極及緩衝層，該緩衝層藉由將無界面活性劑之水性聚苯胺分散液旋塗於雙層陽極上形成。在比較性試驗 Μ中淨化和乾燥的具有雙層陽極之柔韌性pET基材方塊不可由水性聚苯胺分散液〇rmecon® D1002W (2.6重量％於水中_ 的聚苯胺）濕潤，且緩衝層不能用基本與比較性實例A相同之方式由旋塗分散液中無界面活性劑存在的聚苯胺分散液形成。實例21 本實例_說明用一發光二極體獲得的結果，該二極體具有由在基材上金屬層和介電層組成之雙層陽極及緩衝層，該緩衝層藉由將已加入聚氧伸乙基（10)異辛基苯基醚界面活性劑的水性聚苯胺分散液旋塗於陽極上形成。按照比較性試驗Μ之步騾製造發光二極體。發光檢測基本如實例1中所述對該發光二極體進行，結果顯示於表IV中。此結果與比較性試驗μ和Ν之結果比較顯示’本發明之緩衝層使得能夠在發光二極體中於柔韌性基― 材上使用雙層陽極。生試驗〇該比較性試驗說明用一發光二極體得到的結果，該發光 -30- (27) 200304238 二極體具有Λ 丧柔韌性基材上由金屬層和介電層組成的雙層而無本發明之緩衝層。在此*比車父性試驗中使用的柔韌性基材為透明導電薄膜 AgHT4 PET rrn HP溥膜公司獲得，canoga park，CA) 7密耳（180微米）聚（對S太酸乙二醇酯）(pET)片。在該片一侧已先沈積一銀薄膜。介電層已沈積於該銀層上。其具有4歐姆/平方之片電阻。Comparative test N This comparative test illustrates the results obtained when trying to make a light-emitting diode on a flexible substrate. The light-emitting diode has a double-layer anode and a buffer layer consisting of a metal layer and a dielectric layer. The buffer layer is formed by spin-coating a surfactant-free aqueous polyaniline dispersion on a double-layer anode. The flexible pET substrate with a double anode purified and dried in the comparative test M cannot be wetted with an aqueous polyaniline dispersion Ormecon D1002W (2.6% by weight polyaniline in water), and the buffer layer cannot be used. Basically the same way as Comparative Example A was formed from a polyaniline dispersion in which no surfactant was present in the spin-on dispersion. Example 21 This example illustrates the results obtained with a light-emitting diode having a double-layer anode and a buffer layer consisting of a metal layer and a dielectric layer on a substrate. Aqueous polyaniline dispersion of oxyethyl (10) isooctylphenyl ether surfactant is formed by spin coating on the anode. A light emitting diode was manufactured according to the steps of Comparative Test M. Luminescence detection was performed on the light-emitting diode basically as described in Example 1, and the results are shown in Table IV. This result is compared with the results of comparative tests μ and N, which shows that the buffer layer of the present invention enables the use of a double-layer anode on a flexible substrate in a light-emitting diode. This comparative test illustrates the results obtained with a light-emitting diode. The light-emitting -30- (27) 200304238 diode has a double layer consisting of a metal layer and a dielectric layer on a flexible substrate. There is no buffer layer of the present invention. The flexible substrate used in this car specific test is a transparent conductive film AgHT4 PET rrn obtained by HP Membrane Company, Canoga Park, CA) 7 mil (180 micron) poly (p-S-glycol) (pET) tablets. A thin film of silver has been deposited on one side of the sheet. A dielectric layer has been deposited on the silver layer. It has a sheet resistance of 4 ohms / square.

將具有雙層陽極之6英寸XI英寸（15.2釐米X 2.5釐米）PET 片切成1英寸（2 5釐米）方塊。用基本與比較性試驗A中所述· 相同之方式淨化及乾燥此等方塊。按照比較性試驗Μ之步騾製造發光二極體。對該發光二極體進行發光檢測基本如實例1中所述，結果顯示於表IV中。該比較性試驗顯示，具有雙層陽極之柔韌性基材在·無本發明缓衝層下導致發光二極體工作不良。比較性談驗ΡA 6 inch XI inch (15.2 cm x 2.5 cm) PET sheet with a double anode was cut into 1 inch (25 cm) cubes. These blocks were purified and dried in substantially the same manner as described in Comparative Test A. A light emitting diode was manufactured according to the steps of Comparative Test M. The luminescence detection of this light-emitting diode was basically as described in Example 1, and the results are shown in Table IV. This comparative test shows that a flexible substrate with a double-layer anode results in poor operation of the light-emitting diode without the buffer layer of the present invention. Comparative talk

該比較性試驗說明在試圖於柔韌性基材上製造發光二極體時得到的結果，該發光一極體具有由金屬層和介電層組成的雙層陽極及缓衝層’該緩衝層藉由旋塗無界面活性劑之水性聚苯胺分散液形成。在比較性試驗〇中淨化和乾燥的具有雙層陽極之柔韌性 PET基材方塊不可由水性聚苯胺分散液Ormecon® D1002W (2.6重量％於水中的聚苯胺）濕潤，且緩衝層不能用基本與比較性實例A中所述相同之方式由旋塗分散液中無界面活性劑存在的聚苯胺分散液形成° -31 - 200304238 (28)This comparative test illustrates the results obtained when trying to make a light-emitting diode on a flexible substrate, which has a double-layer anode consisting of a metal layer and a dielectric layer and a buffer layer. It is formed by spin-coating an aqueous polyaniline dispersion without surfactant. The flexible PET substrate with a double anode purified and dried in a comparative test 0 cannot be wetted with an aqueous polyaniline dispersion Ormecon® D1002W (2.6% by weight polyaniline in water), and the buffer layer cannot be used with Formed in the same manner as in Comparative Example A from a polyaniline dispersion in the spin-on dispersion without the presence of a surfactant ° -31-200304238 (28)

實例22 本實例說明用一發光二極體獲得的結果，該二極體具有由在柔韌性基材上金屬層和介電層組成之雙層陽極及緩衝層，該緩衝層藉由將已加入聚氧伸乙基（10)異辛基苯基醚界面活性劑的水性聚苯胺分散液旋塗於陽極上形成。基本如實例2 1中所述用在比較性試驗Ο中淨化和乾燥的具有雙層陽極之柔韌性PET基材方塊製備發光二極體，但 Triton® X-100之濃度為在Ormecon® D1002W中小於0.3重量 %Triton® X-100 。發光檢測基本如實例1中所述對該發光二極體進行，結果顯示於表IV中。此結果與比較性試驗0和P之結果比較顯示，本發明之緩衝層使得能夠在發光二極體中於該柔韌性基材上使用雙層陽極。Example 22 This example illustrates the results obtained with a light-emitting diode having a double-layer anode and a buffer layer consisting of a metal layer and a dielectric layer on a flexible substrate. The buffer layer is Aqueous polyaniline dispersion of polyoxyethylene (10) isooctylphenyl ether surfactant is formed by spin coating on the anode. Basically, as described in Example 21, a light-emitting diode was prepared from a flexible PET substrate block with a double-layer anode purified and dried in a comparative test 0, but the concentration of Triton® X-100 was medium or small in Ormecon® D1002W. Based on 0.3% by weight of Triton® X-100. Luminescence detection was performed on the light-emitting diode basically as described in Example 1, and the results are shown in Table IV. This result is shown in comparison with the results of comparative tests 0 and P. The buffer layer of the present invention enables the use of a double-layer anode on the flexible substrate in a light-emitting diode.

表IV 實例或比較性試驗接通電壓 (伏特）光電二極體電流(奈安培） @1毫安培裝置電流裝置電壓(伏特） @1毫安培裝置電流比較性試驗Μ >15 0 … 實例21 4.0 203 6.3 比較性試驗0 14 60 24 實例22 4.0 300 6.7 -32 -Table IV Examples or comparative tests Turn-on voltage (volts) Photodiode current (nanoamperes) @ 1 milliampere device current device voltage (volts) @ 1 milliampere device current comparative test M > 15 0… Example 21 4.0 203 6.3 Comparative test 0 14 60 24 Example 22 4.0 300 6.7 -32-

Claims

200304238 拾、申請專利範國 1. 一種於基材上之發光裝置，該發光裝置包括： (a) 陽極； (b) 陰極； (c) 位於該陽極及該陰極間之活性發射層；以及 (d) 位於該陽極和該活性發射層間之緩衝層，其中該緩衝層由導電聚合物及界面活性劑組成，以該界面活性劑和該導電聚合物之總重量計，該界面活性劑之量係自0.5重量％至15重量％，且該界面活性劑為含氟界面活性劑或聚氧伸乙基烷基驗醚。 2. 根據申請專利範圍第丨項之裝置，其中該界面活性劑為非離子性界面活性劑。 3. 根據申請專利範圍第2項之裝置，其中該非離子性界面活性劑為含氟界面活性劑。 4·根據申請專利範圍第3項之裝置，其中該含氟界面活性劑包έ具式F(CF2CF2)3-8之全氟·燒基。 5.根據申請專利範圍第4項之裝置，其中該含氟界面活性劑為全氟烷基聚氧伸乙基。 6·根據申請專利範圍第3項之裝置，其中該含氟界面活性劑包括氟脂系聚合酯。 7·根據申請專利範圍第2項之裝置，其中該非離子性界面活性劑為聚氧》伸乙基燒基g分酸。 8·根據申請專利範圍第7項之裝置，其中該聚氧伸乙基烷基酴醚為聚氧伸乙基（1〇)異辛基苯基醚。 200304238200304238 Patent application country 1. A light-emitting device on a substrate, the light-emitting device includes: (a) an anode; (b) a cathode; (c) an active emission layer between the anode and the cathode; and (d ) A buffer layer between the anode and the active emission layer, wherein the buffer layer is composed of a conductive polymer and a surfactant, and the amount of the surfactant is based on the total weight of the surfactant and the conductive polymer. 0.5% to 15% by weight, and the surfactant is a fluorine-containing surfactant or polyoxyethylene alkyl ether. 2. The device according to item 丨 of the patent application scope, wherein the surfactant is a non-ionic surfactant. 3. The device according to item 2 of the scope of patent application, wherein the non-ionic surfactant is a fluorine-containing surfactant. 4. The device according to item 3 of the scope of application for a patent, wherein the fluorinated surfactant contains perfluoro · carbon-based radicals of formula F (CF2CF2) 3-8. 5. The device according to item 4 of the scope of patent application, wherein the fluorosurfactant is a perfluoroalkyl polyoxyethylene. 6. The device according to item 3 of the patent application scope, wherein the fluorine-containing surfactant comprises a fluorolipid-based polymer ester. 7. The device according to item 2 of the scope of the patent application, wherein the non-ionic surfactant is polyoxyalkylene glycol. 8. The device according to item 7 of the scope of the application for a patent, wherein the polyoxyethylene alkyl ether is polyoxyethyl (10) isooctylphenyl ether. 200304238

9. 根據申請專利範圍第1項之裝置，其中該含氟界面活性劑為離子性含氟界面活性劑。 10. 根據申請專利範圍第1項之裝置，其中以該界面活性劑和該導電聚合物之總重量計，該界面活性劑之量係自1重量 %至10重量％。 11. 根據申請專利範圍第1項之裝置，其中該導電聚合物為聚苯胺。 12. 根據申請專利範圍第1項之裝置，其中該導電聚合物為聚_ (二氧嘍吩）。 13. 根據申請專利範圍第12項之裝置，其中該聚（二氧嘍吩）為聚（3,4-伸乙基二氧噻吩）。 14. 根據申請專利範圍第1項之裝置，其中該陽極係由包括金屬層和介電層之至少一雙層組成，且其中該至少一介電層係與該緩衝層相鄰。 15. 根據申請專利範圍第14項之裝置，其中該與緩衝層相鄰佈置之至少一介電層係直接位於該緩衝層上。 16. —種於基材上之發光裝置，該發光裝置包括： (a) 陽極； (b) 陰極； (c) 位於該陽極及該陰極間之活性發射層；以及 (d) 位於該陽極和該活性發射層間之緩衝層，其中該緩衝層用一種已加入界面活性劑的導電聚合物之水性分散液形成，該分散液特徵為介於25和35毫牛頓 /米間之表面張力，該導電聚合物之濃度係0.1重量 2003042389. The device according to item 1 of the patent application scope, wherein the fluorine-containing surfactant is an ionic fluorine-containing surfactant. 10. The device according to item 1 of the patent application range, wherein the amount of the surfactant is from 1% to 10% by weight based on the total weight of the surfactant and the conductive polymer. 11. The device according to item 1 of the patent application scope, wherein the conductive polymer is polyaniline. 12. The device according to item 1 of the patent application scope, wherein the conductive polymer is poly (dioxophene). 13. The device according to item 12 of the scope of patent application, wherein the poly (dioxophene) is poly (3,4-ethylenedioxythiophene). 14. The device according to item 1 of the patent application scope, wherein the anode is composed of at least one double layer including a metal layer and a dielectric layer, and wherein the at least one dielectric layer is adjacent to the buffer layer. 15. The device according to item 14 of the patent application, wherein the at least one dielectric layer disposed adjacent to the buffer layer is directly on the buffer layer. 16. A light-emitting device on a substrate, the light-emitting device comprising: (a) an anode; (b) a cathode; (c) an active emission layer between the anode and the cathode; and (d) an anode and The buffer layer between the active emission layers, wherein the buffer layer is formed by an aqueous dispersion of a conductive polymer to which a surfactant has been added, the dispersion is characterized by a surface tension between 25 and 35 millinewtons / meter. Polymer concentration is 0.1 weight 200304238

%至5·ο。/。重量/重量於該分散液中的導電聚合物a 界面活性劑之濃度係小於0.4%重量/重量、d 液中的界面活性劑，且該界面活性劑為含氣界面活性劑或聚氧伸乙基虎基g分醚。 17·根據申請專利範圍第16項之裝置，其中該界面活性劑為非離子性界面活性劑。 18. 根據申請專利範圍第17項之裝置，其中該非離子性界面活性劑為含氟界面活性劑。 19. 根據申請專利範圍第18項之裝置，其中該含氟界面活性劑包含具式F(CF2CF2)3-8之全氟烷基。 20·根據申請專利範圍第19項之裝置，其中該含氟界面活性劑為全氟垸基聚氧伸乙基。 21·根據申請專利範圍第18項之裝置，其中該含氟界面活性劑包括氟脂系聚合酯。 22.根據申請專利範圍第17項之裝置，其中該非離子性界面活性劑為聚氧伸乙基烷基酚醚。 23·根據申請專利範圍第22項之裝置，其中該聚氧伸乙基烷基紛酸為聚氧伸乙基（10)異辛基苯基醚。 24. 根據申請專利範圍第16項之裝置，其中該導電聚合物之 /辰度係0.1至5.0%重量/重量於該分散液中的導電聚合物’具該界面活性劑之濃度係小於〇 3%重量/重量於該分散液中的界面活性劑。 25. 根據申請專利範圍第16項之裝置，其中該導電聚合物為聚苯胺。 200304238% To 5 · ο. /. The concentration of the conductive polymer a surfactant in the dispersion / weight is less than 0.4% by weight / weight, the surfactant in the d solution, and the surfactant is a gas-containing surfactant or polyoxyethylene Glyceryl g is ether. 17. The device according to item 16 of the scope of patent application, wherein the surfactant is a non-ionic surfactant. 18. The device according to item 17 of the scope of patent application, wherein the non-ionic surfactant is a fluorine-containing surfactant. 19. The device according to item 18 of the application, wherein the fluorosurfactant comprises a perfluoroalkyl group having formula F (CF2CF2) 3-8. 20. The device according to item 19 of the application, wherein the fluorine-containing surfactant is a perfluorofluorenyl polyoxyethylene. 21. The device according to item 18 of the scope of patent application, wherein the fluorine-containing surfactant comprises a fluorolipid-based polymer ester. 22. The device according to item 17 of the scope of patent application, wherein the non-ionic surfactant is polyoxyethylene ethyl phenol ether. 23. The device according to item 22 of the scope of patent application, wherein the polyoxyethylidene alkyl acid is polyoxyethyl (10) isooctylphenyl ether. 24. The device according to item 16 of the scope of patent application, wherein the conductive polymer has a concentration of 0.1 to 5.0% by weight / weight of the conductive polymer in the dispersion, and the concentration of the surfactant is less than 0.3. % W / w of surfactant in the dispersion. 25. The device according to item 16 of the application, wherein the conductive polymer is polyaniline. 200304238

26. 根據申請專利範圍第16項之裝置，其中該導電聚合物為聚（二氧噻吩）。 27. 根據申請專利範圍第26項之裝置，其中該聚（二氧噻吩）為聚（3,4-伸乙基二氧嘧吩）。 28. 根據申請專利範圍第16項之裝置，其中該陽極係由氧化錫錮組成。 29. 根據申請專利範圍第16項之裝置，其中該陽極係由至少一雙層組成，該至少一雙層分別包含金屬層及介電層，-其中該至少一介電層係與該緩衝層相鄰。 30. 根據申請專利範圍第29項之裝置，其中該與緩衝層相鄰佈置之至少一介電層係直接位於該緩衝層上。 31. —種用於形成位於發光裝置之陽極和活性發射層間之緩衝層之組合物，該組合物包含一種已加入界面活性劑之導電聚合物之水性分散液，其中該分散液之特徵為介於 25和35毫牛頓/米間之表面張力，該導電聚合物之濃度係 0.1至5.0%重量/重量於該分散液中的導電聚合物，該界面活性劑之濃度係小於0.4%重量/重量於該分散液中的界面活性劑，且該界面活性劑為含氟界面活性劑或聚氧伸乙基烷基酚醚。 32. 根據申請專利範圍第3 1項之組合物，其中該界面活性劑為非離子性界面活性劑。 33. 根據申請專利範圍第32項之組合物，其中該非離子性界面活性劑為含|L界面活性劑。 34. 根據申請專利範圍第33項之組合物，其中該含氟界面活 20030423826. The device according to item 16 of the application, wherein the conductive polymer is poly (dioxythiophene). 27. The device according to item 26 of the scope of patent application, wherein the poly (dioxythiophene) is poly (3,4-ethylidene dioxophene). 28. The device according to item 16 of the application, wherein the anode consists of tin oxide. 29. The device according to item 16 of the scope of patent application, wherein the anode system is composed of at least one double layer, and the at least one double layer includes a metal layer and a dielectric layer, respectively, wherein the at least one dielectric layer and the buffer layer Adjacent. 30. The device according to item 29 of the application, wherein the at least one dielectric layer disposed adjacent to the buffer layer is directly on the buffer layer. 31. A composition for forming a buffer layer between an anode and an active emitting layer of a light emitting device, the composition comprising an aqueous dispersion of a conductive polymer to which a surfactant has been added, wherein the dispersion is characterized by With a surface tension between 25 and 35 mN / m, the concentration of the conductive polymer is 0.1 to 5.0% by weight / weight of the conductive polymer in the dispersion, and the concentration of the surfactant is less than 0.4% by weight / weight The surfactant in the dispersion, and the surfactant is a fluorine-containing surfactant or a polyoxyethylene alkyl phenol ether. 32. The composition according to item 31 of the application, wherein the surfactant is a non-ionic surfactant. 33. The composition according to item 32 of the application, wherein the nonionic surfactant is a surfactant containing L. 34. The composition according to item 33 of the scope of patent application, wherein the fluorine-containing interfacial activity is 200304238

性劑包含具式F(CF2CF2)3_8之全氟烷基。 35. 根據申請專利範圍第34項之組合物，其中該含氟界面活性劑為全氟烷基聚氧伸乙基。 36. 根據申請專利範圍第33項之組合物，其中該含氟界面活性劑包括氟脂系聚合酯。 37·根據申請專利範圍第32項之組合物，其中該非離子性界面；舌性劑為聚氧伸乙基垸基g分酸。 38·根據申凊專利範圍第37項之組合物，其中該聚氧伸乙基· 坑基紛醚為聚氧伸乙基（1〇)異辛基苯基醚。 39·根據申凊專利範圍第3 1項之組合物，其中該導電聚合物之濃度係0.1至5·〇%重量/重量於該分散液中的導電聚合物’該界面活性劑之濃度係小於〇 3%重量/重量於該分散液中的界面活性劑。 4〇·根據申請專利範圍第3 1項之組合物，其中該導電聚合物為聚苯胺。 41·根據申請專利範圍第3丨項之組合物，其中該導電聚合物為聚（二氧噻吩）。 42·根據申请專利範圍第* 1項之組合物，其中該聚（二氧魂吩）為聚（3,4-伸乙基二氧，塞吩）。 43 .根據申請專利範圍第39項之組合物，其中該導電聚合物為聚苯胺。 44. 一種於基材上之發先裝置，該發光裝置包栝： (e) 陽極； (f) 陰極； 200304238 細 (g) 位於該陽極及該陰極間之活性發射層；以及 (h) 位於該陽極和該活性發射層間之緩衝層，其中該緩衝層包括導電聚合物及界面活性劑，以該界面活性劑和該導電聚合物之總重量計，該界面活性劑之量係自0.5重量％至15重量％，且該界面活性劑係選自含氟界面活性劑、聚氧伸乙基烷基酚醚或其混合物。 45. —種於基材上之發光裝置，該發光裝置包括： (e) 陽極； (f) 陰極； (g) 位於該陽極及該陰極間之活性發射層；以及 (h) 位於該陽極和該活性發射層間之緩衝層，其中該緩衝層用一種已加入界面活性劑的導電聚合物之水性分散液形成，該分散液特徵為介於25和35毫牛頓 /米間之表面張力，該導電聚合物之濃度係〇丨至 5.0%重量/重量於該分散液中的導電聚合物，該界面活性劑之濃度係小於0.4%重量/重量於該分散液中的界面活性劑，且該界面活性劑係選自含氟界面活性劑、聚氧伸乙基烷基酚醚或其混合物。 46· —種用於形成位於發光裝置之陽極和活性發射層間之緩衝層之組合物，該組合物包含一種已加入界面活性劑之_ 導電聚合物之水性分散液，其中該分散液之特徵為介於 25和35毫牛頓/米間之表面張力，該導電聚合物之濃度係〇·1至5.0%重量/重量於該分散液中的導電聚合物，該界面The sexual agent comprises a perfluoroalkyl group of formula F (CF2CF2) 3-8. 35. The composition according to item 34 of the application, wherein the fluorosurfactant is a perfluoroalkyl polyoxyethylene. 36. The composition according to claim 33, wherein the fluorosurfactant comprises a fluorolipid polymer ester. 37. The composition according to item 32 of the scope of patent application, wherein the non-ionic interface; the tongue agent is polyoxyethylene ethyl glycol. 38. The composition according to item 37 of the patent application scope, wherein the polyoxyethyl · pityl ether is polyoxyethyl (10) isooctylphenyl ether. 39. The composition according to item 31 of the patent application scope, wherein the concentration of the conductive polymer is 0.1 to 5.0% weight / weight of the conductive polymer in the dispersion. The concentration of the surfactant is less than 03% weight / weight of a surfactant in the dispersion. 40. The composition according to item 31 of the scope of patent application, wherein the conductive polymer is polyaniline. 41. The composition according to item 3 of the patent application scope, wherein the conductive polymer is poly (dioxythiophene). 42. The composition according to item * 1 of the scope of patent application, wherein the poly (dioxophen) is poly (3,4-ethylenedioxy, thiophene). 43. The composition according to claim 39, wherein the conductive polymer is polyaniline. 44. A launch device on a substrate, the light emitting device comprising: (e) an anode; (f) a cathode; 200304238 fine (g) an active emission layer located between the anode and the cathode; and (h) located at A buffer layer between the anode and the active emission layer, wherein the buffer layer includes a conductive polymer and a surfactant, and the amount of the surfactant is from 0.5% by weight based on the total weight of the surfactant and the conductive polymer To 15% by weight, and the surfactant is selected from the group consisting of a fluorine-containing surfactant, a polyoxyethylene alkyl phenol ether, or a mixture thereof. 45. A light-emitting device on a substrate, the light-emitting device comprising: (e) an anode; (f) a cathode; (g) an active emission layer between the anode and the cathode; and (h) an anode and The buffer layer between the active emission layers, wherein the buffer layer is formed by an aqueous dispersion of a conductive polymer to which a surfactant has been added, the dispersion is characterized by a surface tension between 25 and 35 millinewtons / meter. The concentration of the polymer is 0 to 5.0% by weight / weight of the conductive polymer in the dispersion, and the concentration of the surfactant is less than 0.4% by weight / weight of the surfactant in the dispersion, and the interfacial activity is The agent is selected from a fluorine-containing surfactant, polyoxyethylene alkyl phenol ether, or a mixture thereof. 46 · —A composition for forming a buffer layer between an anode and an active emitting layer of a light-emitting device, the composition comprising an aqueous dispersion of a conductive polymer having a surfactant added thereto, wherein the dispersion is characterized by With a surface tension between 25 and 35 mN / m, the concentration of the conductive polymer ranges from 0.1 to 5.0% w / w of the conductive polymer in the dispersion. The interface

200304238 活性劑之濃度係小於0.4%重量/重量於該分散液中的界面活性劑，且該界面活性劑係選自含氟界面活性劑、聚氧伸乙基烷基酚醚或其混合物。 200304238 陸、（一）、本案指定代表圖為：第_圖 (二）、本代表圖之元件代表符號簡單說明：柒、本案若有化學式時，請揭示最能顯示發明特徵的化學式：200304238 The concentration of the active agent is less than 0.4% by weight / weight of the surfactant in the dispersion, and the surfactant is selected from the group consisting of a fluorine-containing surfactant, a polyoxyalkylene phenol ether, or a mixture thereof. 200304238 Lu, (a), the designated representative of the case is: Figure _ (b), the representative symbols of the representative diagram are briefly explained: 柒, if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: